Producing polyolefin products

ABSTRACT

Catalyst systems and methods for making and using the same. A method of polymerizing olefins to produce a polyolefin polymer with a multimodal composition distribution, includes contacting ethylene and a comonomer with a catalyst system. The catalyst system includes a first catalyst compound and a second catalyst compound that are co-supported to form a commonly supported catalyst system. The first catalyst compound includes a compound with the general formula (C 5 H a R 1   b )(C 5 H c R 2   d )HfX 2 . The second catalyst compound includes at least one of the following general formulas: In both catalyst systems, the R groups can be independently selected from any number of substituents, including, for example, H, a hydrocarbyl group, a substituted hydrocarbyl group, or a heteroatom group, among others.

RELATED APPLICATIONS

This application claims the benefit of U.S. Provisional patentapplications having the following serial numbers: Ser. No. 61/938,466,by Ching-Tai Lue et al., filed Feb. 11, 2014 (2014U002.PRV); Ser. No.61/938,472, by Ching-Tai Lue et al., filed Feb. 11, 2014 (2014U003.PRV);Ser. No. 61/981,291, by Francis C. Rix et al., filed Apr. 18, 2014(2014U010.PRV); Ser. No. 61/985,151, by Francis C. Rix et al., filedApr. 28, 2014 (2014U012.PRV); Ser. No. 62/032,383, by Sun-Chueh Kao etal., filed Aug. 1, 2014 (2014U018.PRV); Ser. No. 62/087,905, by FrancisC. Rix et al., filed Dec. 5, 2014 (2014U035.PRV); Ser. No. 62/088,196,by Daniel P. Zilker, Jr. et al., filed Dec. 5, 2014 (2014U036.PRV), Ser.No. 62/087,911, by Ching-Tai Lue et al., filed Dec. 5, 2014(2014U037.PRV), and Ser. No. 62/087,914, by Francis C. Rix et al., filedDec. 5, 2014 (2014U038.PRV), the disclosures of which are incorporatedby reference in their entireties.

BACKGROUND

Ethylene alpha-olefin (polyethylene) copolymers are typically producedin a low pressure reactor, utilizing, for example, solution, slurry, orgas phase polymerization processes. Polymerization takes place in thepresence of catalyst systems such as those employing, for example, aZiegler-Natta catalyst, a chromium based catalyst, a metallocenecatalyst, or combinations thereof.

A number of catalyst compositions containing single site, e.g.,metallocene, catalysts have been used to prepare polyethylenecopolymers, producing relatively homogeneous copolymers at goodpolymerization rates. In contrast to traditional Ziegler-Natta catalystcompositions, single site catalyst compositions, such as metallocenecatalysts, are catalytic compounds in which each catalyst moleculecontains one or only a few polymerization sites. Single site catalystsoften produce polyethylene copolymers that have a narrow molecularweight distribution. Although there are single site catalysts that canproduce broader molecular weight distributions, these catalysts oftenshow a narrowing of the molecular weight distribution as the reactiontemperature is increased, for example, to increase production rates.Further, a single site catalyst will often incorporate comonomer amongthe molecules of the polyethylene copolymer at a relatively uniformrate. The molecular weight distribution and the amount of comonomerincorporation can be used to determine a composition distribution.

The composition distribution of an ethylene alpha-olefin copolymerrefers to the distribution of comonomer, which form short chainbranches, among the molecules that comprise the polyethylene polymer.When the amount of short chain branches varies among the polyethylenemolecules, the resin is said to have a “broad” composition distribution.When the amount of comonomer per 1000 carbons is similar among thepolyethylene molecules of different chain lengths, the compositiondistribution is said to be “narrow”.

The composition distribution is known to influence the properties ofcopolymers, for example, stiffness, toughness, extractable content,environmental stress crack resistance, and heat sealing, among otherproperties. The composition distribution of a polyolefin may be readilymeasured by methods known in the art, for example, Temperature RaisingElution Fractionation (TREF) or Crystallization Analysis Fractionation(CRYSTAF).

It is generally known in the art that a polyolefin's compositiondistribution is largely dictated by the type of catalyst used and istypically invariable for a given catalyst system. Ziegler-Nattacatalysts and chromium based catalysts produce resins with broadcomposition distributions (BCD), whereas metallocene catalysts normallyproduce resins with narrow composition distributions (NCD).

Resins having a broad orthogonal composition distribution (BOCD) inwhich the comonomer is incorporated predominantly in the high molecularweight chains can lead to improved physical properties, for exampletoughness properties and environmental stress crack resistance (ESCR).Because of the improved physical properties of resins with orthogonalcomposition distributions needed for commercially desirable products,there exists a need for controlled techniques for forming polyethylenecopolymers having a broad orthogonal composition distribution.

SUMMARY

An exemplary embodiment described herein provides a method ofpolymerizing olefins to produce a polyolefin polymer with a multimodalcomposition distribution, including contacting ethylene and a comonomerwith a catalyst system. The catalyst system includes a first catalystcompound and a second catalyst compound that are co-supported to form acommonly supported catalyst system. The first catalyst compound includesa compound with the following formula:

(C₅H_(a)R¹ _(b))(C₅H_(c)R² _(d))HfX₂.

In this formula, each R¹ is independently H, a hydrocarbyl group, asubstituted hydrocarbyl group, or a heteroatom group; each R² isindependently H, a hydrocarbyl group, a substituted hydrocarbyl group,or a heteroatom group; a and c are ≧3; a+b=c+d=5; at least one R¹ and atleast one R² is a hydrocarbyl or substituted hydrocarbyl group; adjacentgroups R¹ and R² groups may be coupled to form a ring; and each X isindependently a leaving group selected from a labile hydrocarbyl,substituted hydrocarbyl, or heteroatom group, or a divalent radical thatlinks to an R¹ or R² group. The second catalyst compound includes atleast one of the following formulas:

In this formula, each R³ is independently H, a hydrocarbyl group, asubstituted hydrocarbyl group, or a heteroatom group; R⁴ is ahydrocarbyl group, a substituted hydrocarbyl group, or a heteoatomgroup; each R⁵ is independently H, a hydrocarbyl group, a substitutedhydrocarbyl group, or a heteroatom group; wherein R³, R⁴, and R⁵ may bethe same or different; wherein R³, R⁴, or R⁵ groups may be joined withR³, R⁴, or R⁵ groups on an opposing cyclopentadienyl structure to formone or more bridges if the number of atoms connecting the twocyclopentadienyl rings is ≧3; and each X is independently a leavinggroup selected from a labile hydrocarbyl, substituted hydrocarbyl, orheteroatom group.

Another embodiment provides a catalyst composition including a firstcatalyst compound and a second catalyst compound that are co-supportedforming a commonly supported catalyst system. The first catalystcompound includes a compound with the following formula:

(C₅H_(a)R¹ _(b))(C₅H_(c)R² _(d))HfX₂.

In this formula, each R¹ is independently H, a hydrocarbyl group, asubstituted hydrocarbyl group, or a heteroatom group; each R² isindependently a H, hydrocarbyl group, a substituted hydrocarbyl group,or a heteroatom group; a and c are ≧3; a+b=c+d=5; at least one R¹ and atleast one R² is a hydrocarbyl or substituted hydrocarbyl group; adjacentgroups R¹ and R² groups may be coupled to form a ring; and each X isindependently a leaving group selected from a labile hydrocarbyl,substituted hydrocarbyl, or heteroatom group, or a divalent radical thatlinks to an R¹ or R² group. The second catalyst compound includes atleast one of the following formulas:

In this formula, each R³ is independently H, a hydrocarbyl group, asubstituted hydrocarbyl group, or a heteroatom group; R⁴ is ahydrocarbyl group, a substituted hydrocarbyl group, or a heteoatomgroup; each R⁵ is independently H, a hydrocarbyl group, a substitutedhydrocarbyl group, or a heteroatom group; wherein R³, R⁴, and R⁵ may bethe same or different; wherein R³, R⁴, or R⁵ groups may be joined withR³, R⁴, or R⁵ groups on an opposing cyclopentadienyl structure to formone or more bridges if the number of atoms connecting the twocyclopentadienyl rings is ≧3; and each X is independently a leavinggroup selected from a labile hydrocarbyl, substituted hydrocarbyl, orheteroatom group. X may be a divalent radical that links to a R³, R⁴, orR⁵ substituent.

BRIEF DESCRIPTION OF THE DRAWINGS

FIG. 1 is a schematic of a gas-phase reactor system, showing theaddition of at least two catalysts, at least one of which is added as atrim catalyst.

FIG. 2 is a plot of a series of polymers that were prepared to test therelative abilities of a series of metallocene catalysts to prepare aresin having about a 1 melt index (MI) and a density (D) of about 0.92.

FIG. 3 is a plot of the series of polymers of FIG. 2, showing the meltindex ratio (MIR) of the series of polymers made by differentmetallocene (MCN) catalysts.

FIG. 4 is a flow chart of a method for making a co-supportedpolymerization catalyst.

DETAILED DESCRIPTION

It has been discovered that when a support is impregnated with multiplecatalysts, new polymeric materials with an improved balance ofstiffness, toughness and processibility can be achieved, e.g., bycontrolling the amounts and types of catalysts present on the support.As described in embodiments herein, an appropriate selection of thecatalysts and ratios may be used to adjust the molecular weightdistribution (MWD), short chain branch distribution (SCBD), andlong-chain branch distribution (LCBD) of the polymer, for example, toprovide a polymer with a broad orthogonal composition distribution(BOCD). The MWD, SCBD, and LCBDs would be controlled by combiningcatalysts with the appropriate weight average molecular weight (Mw),comonomer incorporation, and long chain branching (LCB) formation underthe conditions of the polymerization.

Employing multiple pre-catalysts that are co-supported on a singlesupport mixed with an activator, such as a silica methylaluminoxane(SMAO), can provide a cost advantage by making the product in onereactor instead of multiple reactors. Further, using a single supportalso ensures intimate mixing of the polymers and offers improvedoperability relative to preparing a mixture of polymers of different Mwand density independently from multiple catalysts in a single reactor.As used herein, a pre-catalyst is a catalyst compound prior to exposureto activator.

As an example, for linear low-density polyethylene film (LLDPE) filmapplications, it would be desirable to prepare an ethylene hexenecopolymer with a molecular weight of between about 90 Kg/mol and 110Kg/mol, or about 100 Kg/mol and an average density of between about 0.9and 0.925, or about 0.918. The typical MWD for linear metallocene resinsis 2.5-3.5. Blend studies indicate that it would be desirable to broadenthis distribution by employing two catalysts that each providesdifferent average molecular weights. The ratio of the Mw for the lowmolecular weight component and the high molecular weight component wouldbe between 1:1 and 1:10, or about 1:2 and 1:5.

The density of a polyethylene copolymer provides an indication of theincorporation of comonomer into a polymer, with lower densitiesindicating higher incorporation. The difference in the densities of thelow molecular weight (LMW) component and the high molecular weight (HMW)component would preferably be greater than about 0.02, or greater thanabout 0.04 with the HMW component having a lower density than the LMWcomponent. For two resins with Mw of 25 Kg/mol and 125 Kg/mol, thedifference in density requires around around a 1.5:1 or preferably about2:1, or more preferably about 3:1 or more preferably a 4:1 or even agreater than 4:1 difference difference in comonomer incorporationability. It is also desirable to minimize the level of long chainbranching (LCB) in the polymer as that provides strong orientation infilm fabrication which imbalances MD/TD tear and reduces toughness.

These factors can be adjusted by controlling the MWD and SCBD, which, inturn, can be adjusted by changing the relative amount of the twopre-catalysts on the support. This may be adjusted during the formationof the pre-catalysts, for example, by supporting two catalysts on asingle support. In some embodiments, the relative amounts of thepre-catalysts can be adjusted by adding one of the components to acatalyst mixture en-route to the reactor in a process termed “trim.”Feedback of polymer property data can be used to control the amount ofcatalyst addition. Metallocenes (MCNs) are known to trim well with othercatalysts.

Further, a variety of resins with different MWD, SCBD, and LCBD may beprepared from a limited number of catalysts. To perform this function,the pre-catalysts should trim well onto activator supports. Twoparameters that benefit this are solubility in alkane solvents and rapidsupportation on the catalyst slurry en-route to the reactor. This favorsthe use of MCNs to achieve controlled MWD, SCBD, and LCBD. Techniquesfor selecting catalysts that can be used to generate targeted molecularweight compositions, including BOCD polymer systems, are disclosedherein.

Various catalyst systems and components may be used to generate thepolymers and molecular weight compositions disclosed. These arediscussed in the sections to follow. The first section discussescatalyst compounds that can be used in embodiments. The second sectiondiscusses generating catalyst slurrys that may be used for implementingthe techniques described. The third section discusses catalyst supportsthat may be used. The fourth section discusses catalyst activators thatmay be used. The fifth section discusses the catalyst componentsolutions that may be used to add additional catalysts in trim systems.Gas phase polymerizations may use static control or continuity agents,which are discussed in the sixth section. A gas-phase polymerizationreactor with a trim feed system is discussed in the seventh section. Theuse of the catalyst composition to control product properties isdiscussed in an eighth section and an exemplary polymerization processis discussed in a ninth section. Examples of the implementation of theprocedures discussed is incorporated into a tenth section.

Catalyst Compounds

Metallocene Catalyst Compounds

Metallocene catalyst compounds can include “half sandwich” and/or “fullsandwich” compounds having one or more Cp ligands (cyclopentadienyl andligands isolobal to cyclopentadienyl) bound to at least one Group 3 toGroup 12 metal atom, and one or more leaving group(s) bound to the atleast one metal atom. As used herein, all reference to the PeriodicTable of the Elements and groups thereof is to the NEW NOTATIONpublished in HAWLEY'S CONDENSED CHEMICAL DICTIONARY, Thirteenth Edition,John Wiley & Sons, Inc., (1997) (reproduced there with permission fromIUPAC), unless reference is made to the Previous IUPAC form noted withRoman numerals (also appearing in the same), or unless otherwise noted.

The Cp ligands are one or more rings or ring system(s), at least aportion of which includes π-bonded systems, such as cycloalkadienylligands and heterocyclic analogues. The ring(s) or ring system(s)typically include atoms selected from the group consisting of Groups 13to 16 atoms, and, in a particular exemplary embodiment, the atoms thatmake up the Cp ligands are selected from the group consisting of carbon,nitrogen, oxygen, silicon, sulfur, phosphorous, germanium, boron,aluminum, and combinations thereof, where carbon makes up at least 50%of the ring members. In a more particular exemplary embodiment, the Cpligand(s) are selected from the group consisting of substituted andunsubstituted cyclopentadienyl ligands and ligands isolobal tocyclopentadienyl, non-limiting examples of which includecyclopentadienyl, indenyl, fluorenyl and other structures. Furthernon-limiting examples of such ligands include cyclopentadienyl,cyclopentaphenanthreneyl, indenyl, benzindenyl, fluorenyl,octahydrofluorenyl, cyclooctatetraenyl, cyclopentacyclododecene,phenanthrindenyl, 3,4-benzofluorenyl, 9-phenylfluorenyl,8-H-cyclopent[a]acenaphthylenyl, 7-H-dibenzofluorenyl,indeno[1,2-9]anthrene, thiophenoindenyl, thiophenofluorenyl,hydrogenated versions thereof (e.g., 4,5,6,7-tetrahydroindenyl, or “H₄Ind”), substituted versions thereof (as discussed and described in moredetail below), and heterocyclic versions thereof.

The metal atom “M” of the metallocene catalyst compound can be selectedfrom the group consisting of Groups 3 through 12 atoms and lanthanideGroup atoms in one exemplary embodiment; and selected from the groupconsisting of Groups 3 through 10 atoms in a more particular exemplaryembodiment, and selected from the group consisting of Sc, Ti, Zr, Hf, V,Nb, Ta, Mn, Re, Fe, Ru, Os, Co, Rh, Ir, and Ni in yet a more particularexemplary embodiment; and selected from the group consisting of Groups4, 5, and 6 atoms in yet a more particular exemplary embodiment, and Ti,Zr, Hf atoms in yet a more particular exemplary embodiment, and Hf inyet a more particular exemplary embodiment. The oxidation state of themetal atom “M” can range from 0 to +7 in one exemplary embodiment; andin a more particular exemplary embodiment, can be +1, +2, +3, +4, or +5;and in yet a more particular exemplary embodiment can be +2, +3 or +4.The groups bound to the metal atom “M” are such that the compoundsdescribed below in the formulas and structures are electrically neutral,unless otherwise indicated. The Cp ligand forms at least one chemicalbond with the metal atom M to form the “metallocene catalyst compound.”The Cp ligands are distinct from the leaving groups bound to thecatalyst compound in that they are not highly susceptible tosubstitution/abstraction reactions.

The one or more metallocene catalyst compounds can be represented by theformula (I):

Cp^(A)Cp^(B)MX_(n)  (I)

in which M is as described above; each X is chemically bonded to M; eachCp group is chemically bonded to M; and n is 0 or an integer from 1 to4, and either 1 or 2 in a particular exemplary embodiment.

The ligands represented by Cp^(A) and Cp^(B) in formula (I) can be thesame or different cyclopentadienyl ligands or ligands isolobal tocyclopentadienyl, either or both of which can contain heteroatoms andeither or both of which can be substituted by a group R. In at least onespecific embodiment, Cp^(A) and Cp^(B) are independently selected fromthe group consisting of cyclopentadienyl, indenyl, tetrahydroindenyl,fluorenyl, and substituted derivatives of each.

Independently, each Cp^(A) and Cp^(B) of formula (I) can beunsubstituted or substituted with any one or combination of substituentgroups R. Non-limiting examples of substituent groups R as used instructure (I) as well as ring substituents in structures Va-d, discussedand described below, include groups selected from the group consistingof hydrogen radicals, alkyls, alkenyls, alkynyls, cycloalkyls, aryls,acyls, aroyls, alkoxys, aryloxys, alkylthiols, dialkylamines,alkylamidos, alkoxycarbonyls, aryloxycarbonyls, carbomoyls, alkyl- anddialkyl-carbamoyls, acyloxys, acylaminos, aroylaminos, and combinationsthereof. More particular non-limiting examples of alkyl substituents Rassociated with formulas (I) through (Va-d) include methyl, ethyl,propyl, butyl, pentyl, hexyl, cyclopentyl, cyclohexyl, benzyl, phenyl,methylphenyl, and tert-butylphenyl groups and the like, including alltheir isomers, for example, tertiary-butyl, isopropyl, and the like.

As used herein, and in the claims, hydrocarbyl substituents, or groups,are made up of between 1 and 100 or more carbon atoms, the remainderbeing hydrogen. Non-limiting examples of hydrocarbyl substituentsinclude linear or branched or cyclic: alkyl radicals; alkenyl radicals;alkynyl radicals; cycloalkyl radicals; aryl radicals; alkylene radicals,or a combination thereof. Non-limiting examples include methyl, ethyl,propyl, butyl, pentyl, hexyl, cyclopentyl, cyclohexyl; olefinicallyunsaturated substituents including vinyl-terminated ligands (for examplebut-3-enyl, prop-2-enyl, hex-5-enyl and the like), benzyl or phenylgroups and the like, including all their isomers, for example tertiarybutyl, isopropyl, and the like.

As used herein, and in the claims, substituted hydrocarbyl substituents,or groups, are made up of between 1 and 100 or more carbon atoms, theremainder being hydrogen, fluorine, chlorine, bromine, iodine, oxygen,sulfur, nitrogen, phosphorous, boron, silicon, germanium or tin atoms orother atom systems tolerant of olefin polymerization systems.Substituted hydrocarbyl substituents are carbon based radicals.Non-limiting examples of substituted hydrocarbyl substituentstrifluoromethyl radical, trimethylsilanemethyl (Me3SiCH 2-) radicals.

As used herein, and in the claims, heteroatom substituents, or groups,are fluorine, chlorine, bromine, iodine, oxygen, sulfur, nitrogen,phosphorous, boron, silicon, germanium or tin based radicals. They maybe the heteroatom atom by itself. Further, heteroatom substituentsinclude organometalloid radicals. Non-limiting examples of heteroatomsubstituents include chloro radicals, fluoro radicals, methoxy radicals,diphenyl amino radicals, thioalkyls, thioalkenyls, trimethylsilylradicals, dimethyl aluminum radicals, alkoxydihydrocarbylsilyl radicals,siloxydiydrocabylsilyl radicals, tris(perflourophenyl)boron and thelike.

Other possible radicals include substituted alkyls and aryls such as,for example, fluoromethyl, fluroethyl, difluroethyl, iodopropyl,bromohexyl, chlorobenzyl, hydrocarbyl substituted organometalloidradicals including trimethylsilyl, trimethylgermyl, methyldiethylsilyl,and the like, and halocarbyl-substituted organometalloid radicals,including tris(trifluoromethyl)silyl, methylbis(difluoromethyl)silyl,bromomethyldimethylgermyl and the like; and disubstituted boron radicalsincluding dimethylboron, for example; and disubstituted Group 15radicals including dimethylamine, dimethylphosphine, diphenylamine,methylphenylphosphine, as well as Group 16 radicals including methoxy,ethoxy, propoxy, phenoxy, methylsulfide and ethylsulfide. Othersubstituent groups R include, but are not limited to, olefins such asolefinically unsaturated substituents including vinyl-terminated ligandssuch as, for example, 3-butenyl, 2-propenyl, 5-hexenyl, and the like. Inone exemplary embodiment, at least two R groups (two adjacent R groupsin a particular exemplary embodiment) are joined to form a ringstructure having from 3 to 30 atoms selected from the group consistingof carbon, nitrogen, oxygen, phosphorous, silicon, germanium, aluminum,boron, and combinations thereof. Also, a substituent group R such as1-butanyl can form a bonding association to the element M.

Each X in the formula (I) above and for the formula/structures (II)through (Va-d) below is independently selected from the group consistingof: any leaving group, in one exemplary embodiment; halogen ions,hydrides, C₁ to C₁₂ alkyls, C₂ to C₁₂ alkenyls, C₆ to C₁₂ aryls, C₇ toC₂₀ alkylaryls, C₁ to C₁₂ alkoxys, C₆ to C₁₆ aryloxys, C₇ to C₈alkylaryloxys, C₁ to C₁₂ fluoroalkyls, C₆ to C₁₂ fluoroaryls, and C₁ toC₁₂ heteroatom-containing hydrocarbons and substituted derivativesthereof, in a more particular exemplary embodiment; hydride, halogenions, C₁ to C₆ alkyls, C₂ to C₆ alkenyls, C₇ to C₁₈ alkylaryls, C₁ to C₆alkoxys, C₆ to C₁₄ aryloxys, C₇ to C₁₆ alkylaryloxys, C₁ to C₆alkylcarboxyla yield a new polymerization catalyst tes, C₁ to C₆fluorinated alkylcarboxylates, C₆ to C₁₂ arylcarboxylates, C₇ to C₁₈alkylarylcarboxylates, C₁ to C₆ fluoroalkyls, C₂ to C₆ fluoroalkenyls,and C₇ to C₁₈ fluoroalkylaryls in yet a more particular exemplaryembodiment; hydride, chloride, fluoride, methyl, phenyl, phenoxy,benzoxy, tosyl, fluoromethyls and fluorophenyls, in yet a moreparticular exemplary embodiment; C₁ to C₁₂ alkyls, C₂ to C₁₂ alkenyls,C₆ to C₁₂ aryls, C₇ to C₂₀ alkylaryls, substituted C₁ to C₁₂ alkyls,substituted C₆ to C₁₂ aryls, substituted C₇ to C₂₀ alkylaryls and C₁ toC₁₂ heteroatom-containing alkyls, C₁ to C₁₂ heteroatom-containing aryls,and C₁ to C₁₂ heteroatom-containing alkylaryls, in yet a more particularexemplary embodiment; chloride, fluoride, C₁ to C₆ alkyls, C₂ to C₆alkenyls, C₇ to C₁₈ alkylaryls, halogenated C₁ to C₆ alkyls, halogenatedC₂ to C₆ alkenyls, and halogenated C₇ to C₁₈ alkylaryls, in yet a moreparticular exemplary embodiment; fluoride, methyl, ethyl, propyl,phenyl, methylphenyl, dimethylphenyl, trimethylphenyl, fluoromethyls(mono-, di- and trifluoromethyls) and fluorophenyls (mono-, di-, tri-,tetra- and pentafluorophenyls), in yet a more particular exemplaryembodiment; and fluoride, in yet a more particular exemplary embodiment.

Other non-limiting examples of X groups include amines, phosphines,ethers, carboxylates, dienes, hydrocarbon radicals having from 1 to 20carbon atoms, fluorinated hydrocarbon radicals (e.g., —C₆F₅(pentafluorophenyl)), fluorinated alkylcarboxylates (e.g., CF₃C(O)O⁻),hydrides, halogen ions and combinations thereof. Other examples of Xligands include alkyl groups such as cyclobutyl, cyclohexyl, methyl,heptyl, tolyl, trifluoromethyl, tetramethylene, pentamethylene,methylidene, methyoxy, ethyoxy, propoxy, phenoxy, bis(N-methylanilide),dimethylamide, dimethylphosphide radicals and the like. In one exemplaryembodiment, two or more X's form a part of a fused ring or ring system.In at least one specific embodiment, X can be a leaving group selectedfrom the group consisting of chloride ions, bromide ions, C₁ to C₁₀alkyls, and C₂ to C₁₂ alkenyls, carboxylates, acetylacetonates, andalkoxides.

The metallocene catalyst compound includes those of formula (I) whereCp^(A) and Cp^(B) are bridged to each other by at least one bridginggroup, (A), such that the structure is represented by formula (II):

Cp^(A)(A)Cp^(B)MX_(n)  (II)

These bridged compounds represented by formula (II) are known as“bridged metallocenes.” The elements Cp^(A), Cp^(B), M, X and n instructure (II) are as defined above for formula (I); where each Cpligand is chemically bonded to M, and (A) is chemically bonded to eachCp. The bridging group (A) can include divalent hydrocarbon groupscontaining at least one Group 13 to 16 atom, such as, but not limitedto, at least one of a carbon, oxygen, nitrogen, silicon, aluminum,boron, germanium, tin atom, and combinations thereof; where theheteroatom can also be C₁ to C₁₂ alkyl or aryl substituted to satisfyneutral valency. In at least one specific embodiment, the bridging group(A) can also include substituent groups R as defined above (for formula(I)) including halogen radicals and iron. In at least one specificembodiment, the bridging group (A) can be represented by C₁ to C₆alkylenes, substituted C₁ to C₆ alkylenes, oxygen, sulfur, R′₂C═,R′₂Si═, ═Si(R′)₂Si(R′₂)═, R′₂Ge═, and R′P═, where “=” represents twochemical bonds, R′ is independently selected from the group consistingof hydride, hydrocarbyl, substituted hydrocarbyl, halocarbyl,substituted halocarbyl, hydrocarbyl-substituted organometalloid,halocarbyl-substituted organometalloid, disubstituted boron,disubstituted Group 15 atoms, substituted Group 16 atoms, and halogenradical; and where two or more R′ can be joined to form a ring or ringsystem. In at least one specific embodiment, the bridged metallocenecatalyst compound of formula (II) includes two or more bridging groups(A). In one or more embodiments, (A) can be a divalent bridging groupbound to both Cp^(A) and Cp^(B) selected from the group consisting ofdivalent C₁ to C₂₀ hydrocarbyls and C₁ to C₂₀ heteroatom containinghydrocarbonyls, where the heteroatom containing hydrocarbonyls includefrom one to three heteroatoms.

The bridging group (A) can include methylene, ethylene, ethylidene,propylidene, isopropylidene, diphenylmethylene, 1,2-dimethylethylene,1,2-diphenylethylene, 1,1,2,2-tetramethylethylene, dimethylsilyl,diethylsilyl, methyl-ethylsilyl, trifluoromethylbutylsilyl,bis(trifluoromethyl)silyl, di(n-butyl)silyl, di(n-propyl)silyl,di(i-propyl)silyl, di(n-hexyl)silyl, dicyclohexylsilyl, diphenylsilyl,cyclohexylphenylsilyl, t-butylcyclohexylsilyl, di(t-butylphenyl)silyl,di(p-tolyl)silyl, and the corresponding moieties where the Si atom isreplaced by a Ge or a C atom; as well as dimethylsilyl, diethylsilyl,dimethylgermyl and diethylgermyl. The bridging group (A) can alsoinclude —Si(hydrocarbyl)2-O-(hydrocarbyl)2Si——Si(substitutedhydrocarbyl)2-O-(substitutedhydrocarbyl)2Si— groups andthe like such as —SiMe2-O—SiMe2- and —SiPh2-O—SiPh2-.

The bridging group (A) can also be cyclic, having, for example, 4 to 10ring members; in a more particular exemplary embodiment, bridging group(A) can have 5 to 7 ring members. The ring members can be selected fromthe elements mentioned above, and, in a particular embodiment, can beselected from one or more of B, C, Si, Ge, N, and O. Non-limitingexamples of ring structures which can be present as, or as part of, thebridging moiety are cyclobutylidene, cyclopentylidene, cyclohexylidene,cycloheptylidene, cyclooctylidene and the corresponding rings where oneor two carbon atoms are replaced by at least one of Si, Ge, N and O. Inone or more embodiments, one or two carbon atoms can be replaced by atleast one of Si and Ge. The bonding arrangement between the ring and theCp groups can be cis-, trans-, or a combination thereof.

The cyclic bridging groups (A) can be saturated or unsaturated and/orcan carry one or more substituents and/or can be fused to one or moreother ring structures. If present, the one or more substituents can be,in at least one specific embodiment, selected from the group consistingof hydrocarbyl (e.g., alkyl, such as methyl) and halogen (e.g., F, Cl).The one or more Cp groups to which the above cyclic bridging moietiescan optionally be fused can be saturated or unsaturated, and areselected from the group consisting of those having 4 to 10, moreparticularly 5, 6, or 7 ring members (selected from the group consistingof C, N, O, and S in a particular exemplary embodiment) such as, forexample, cyclopentyl, cyclohexyl and phenyl. Moreover, these ringstructures can themselves be fused such as, for example, in the case ofa naphthyl group. Moreover, these (optionally fused) ring structures cancarry one or more substituents. Illustrative, non-limiting examples ofthese substituents are hydrocarbyl (particularly alkyl) groups andhalogen atoms. The ligands Cp^(A) and Cp^(B) of formula (I) and (II) canbe different from each other. The ligands Cp^(A) and Cp^(B) of formula(I) and (II) can be the same. The metallocene catalyst compound caninclude bridged mono-ligand metallocene compounds (e.g., monocyclopentadienyl catalyst components).

It is contemplated that the metallocene catalyst components discussedand described above include their structural or optical or enantiomericisomers (racemic mixture), and, in one exemplary embodiment, can be apure enantiomer. As used herein, a single, bridged, asymmetricallysubstituted metallocene catalyst compound having a racemic and/or mesoisomer does not, itself, constitute at least two different bridged,metallocene catalyst components.

As noted above, the amount of the transition metal component of the oneor more metallocene catalyst compounds in the catalyst system can rangefrom a low of about 0.0.01 wt. %, about 0.2 wt %, about 3 wt. %, about0.5 wt. %, or about 0.7 wt. % to a high of about 1 wt. %, about 2 wt. %,about 2.5 wt. %, about 3 wt. %, about 3.5 wt. %, or about 4 wt. %, basedon the total weight of the catalyst system.

The “metallocene catalyst compound” can include any combination of any“embodiment” discussed and described herein. For example, themetallocene catalyst compound can include, but is not limited to,bis(n-propylcyclopentadienyl) hafnium (CH₃)₂,bis(n-propylcyclopentadienyl) hafnium F₂, bis(n-propylcyclopentadienyl)hafnium Cl₂, or bis(n-butyl, methyl cyclopentadienyl) zirconium Cl₂, orany combination thereof.

Other metallocene catalyst compounds that may be used are supportedconstrained geometry catalysts (sCGC) that include (a) an ionic complex,(b) a transition metal compound, (c) an organometal compound, and (d) asupport material. In some embodiments, the sCGC catalyst may include aborate ion. The borate anion is represented by the formula[BQ_(4-z′)(G_(q)(T-H)_(r))_(z′)]^(d-), wherein: B is boron in a valencestate of 3; Q is selected from the group consisting of hydride,dihydrocarbylamido, halide, hydrocarbyloxide, hydrocarbyl, andsubstituted-hydrocarbyl radicals; z′ is an integer in a range from 1 to4; G is a polyvalent hydrocarbon radical having r+1 valencies bonded toM′ and r groups (T-H); q is an integer, 0 or 1; the group (T-H) is aradical wherein T includes O, S, NR, or PR, the O, S, N or P atom ofwhich is bonded to hydrogen atom H, wherein R is a hydrocarbyl radical,a trihydrocarbylsilyl radical, a trihydrocarbyl germyl radical orhydrogen; r is an integer from 1 to 3; and d is 1. Alternatively theborate ion may be representative by the formula[BQ_(4-z′)(G_(q)(T-M^(o)R^(C) _(x-1)X^(a) _(y))_(r))_(z′)]^(d-),wherein: B is boron in a valence state of 3; Q is selected from thegroup consisting of hydride, dihydrocarbylamido, halide,hydrocarbyloxide, hydrocarbyl, and substituted-hydrocarbyl radicals; z′is an integer in a range from 1 to 4; G is a polyvalent hydrocarbonradical having r+1 valencies bonded to B and r groups (T-M^(o)R^(C)_(x-1)X^(a) _(y)); q is an integer, 0 or 1; the group (T-M^(o)R^(C)_(x-1)X^(a) _(y)) is a radical wherein T includes O, S, NR, or PR, theO, S, N or P atom of which is bonded to M°, wherein R is a hydrocarbylradical, a trihydrocarbylsilyl radical, a trihydrocarbyl germyl radicalor hydrogen; M° is a metal or metalloid selected from Groups 1-14 of thePeriodic Table of the Elements, R^(C) independently each occurrence ishydrogen or a group having from 1 to 80 nonhydrogen atoms which ishydrocarbyl, hydrocarbylsilyl, or hydrocarbylsilylhydrocarbyl; X^(a) isa noninterfering group having from 1 to 100 nonhydrogen atoms which ishalo-substituted hydrocarbyl, hydrocarbylamino-substituted hydrocarbyl,hydrocarbyloxy-substituted hydrocarbyl, hydrocarbylamino,di(hydrocarbyl)amino, hydrocarbyloxy or halide; x is a nonzero integerwhich may range from 1 to an integer equal to the valence of M°; y iszero or a nonzero integer which may range from 1 to an integer equal to1 less than the valence of M°; and x+y equals the valence of M°; r is aninteger from 1 to 3; and d is 1. In some embodiments, the borate ion maybe of the above described formulas where z′ is 1 or 2, q is 1, and r is1.

The catalyst system can include other single site catalysts such asGroup 15-containing catalysts. The catalyst system can include one ormore second catalysts in addition to the single site catalyst compoundsuch as chromium-based catalysts, Ziegler-Natta catalysts, one or moreadditional single-site catalysts such as metallocenes or Group15-containing catalysts, bimetallic catalysts, and mixed catalysts. Thecatalyst system can also include AlCl₃, cobalt, iron, palladium, or anycombination thereof.

Examples of structures of MCN compounds that may be used in embodimentsinclude the hafnium compound shown as formula (III), the zirconiumcompounds shown as formulas (IV-A-C), and bridged zirconium compounds,shown as formulas (V-A-B).

Although these compounds are shown with methyl- and chloro-groupsattached to the central metal, it can be understood that these groupsmay be different without changing the catalyst involved. For example,each of these substituents may independently be a methyl group (Me), achloro group (Cl), a fluoro group (F), or any number of other groups,including organic groups, or heteroatom groups. Further, thesesubstituents will change during the reaction, as a pre-catalyst isconverted to the active catalyst for the reaction. Further, any numberof other substituents may be used on the ring structures, including anyof the substituents described above with respect to formulas (I) and(II).

Group 15 Atom and Metal-Containing Catalyst Compounds

The catalyst system can include one or more Group 15 metal-containingcatalyst compounds, such as [(2,3,4,5,6 Me₅C₆N)CH₂CH₂]₂NHZrBn₂, where Bnis a benzyl group. The Group 15 metal-containing compound generallyincludes a Group 3 to 14 metal atom, a Group 3 to 7, or a Group 4 to 6metal atom. In many embodiments, the Group 15 metal-containing compoundincludes a Group 4 metal atom bound to at least one leaving group andalso bound to at least two Group 15 atoms, at least one of which is alsobound to a Group 15 or 16 atom through another group.

In one or more embodiments, at least one of the Group 15 atoms is alsobound to a Group 15 or 16 atom through another group which may be a C₁to C₂₀ hydrocarbon group, a heteroatom containing group, silicon,germanium, tin, lead, or phosphorus, wherein the Group 15 or 16 atom mayalso be bound to nothing or a hydrogen, a Group 14 atom containinggroup, a halogen, or a heteroatom containing group, and wherein each ofthe two Group 15 atoms are also bound to a cyclic group and canoptionally be bound to hydrogen, a halogen, a heteroatom or ahydrocarbyl group, or a heteroatom containing group.

The Group 15-containing metal compounds can be described moreparticularly with formulas (VI) or (VII):

in which M is a Group 3 to 12 transition metal or a Group 13 or 14 maingroup metal, a Group 4, 5, or 6 metal. In many embodiments, M is a Group4 metal, such as zirconium, titanium or hafnium. Each X is independentlya leaving group, such as an anionic leaving group. The leaving group mayinclude a hydrogen, a hydrocarbyl group, a heteroatom, a halogen, or analkyl; y is 0 or 1 (when y is 0 group L′ is absent). The term ‘n’ is theoxidation state of M. In various embodiments, n is +3, +4, or +5. Inmany embodiments, n is +4. The term ‘m’ represents the formal charge ofthe YZL or the YZL′ ligand, and is 0, −1, −2 or −3 in variousembodiments. In many embodiments, m is −2. L is a Group 15 or 16element, such as nitrogen; L′ is a Group 15 or 16 element or Group 14containing group, such as carbon, silicon or germanium. Y is a Group 15element, such as nitrogen or phosphorus. In many embodiments, Y isnitrogen. Z is a Group 15 element, such as nitrogen or phosphorus. Inmany embodiments, Z is nitrogen. R¹ and R² are, independently, a C₁ toC₂₀ hydrocarbon group, a heteroatom containing group having up to twentycarbon atoms, silicon, germanium, tin, lead, or phosphorus. In manyembodiments, R¹ and R² are a C₂ to C₂₀ alkyl, aryl, or aralkyl group,such as a linear, branched, or cyclic C₂ to C₂₀ alkyl group, or a C₂ toC₆ hydrocarbon group. R¹ and R² may also be interconnected to eachother. R³ may be absent or may be a hydrocarbon group, a hydrogen, ahalogen, a heteroatom containing group. In many embodiments, R³ isabsent or a hydrogen, or a linear, cyclic or branched alkyl group having1 to 20 carbon atoms. R⁴ and R⁵ are independently an alkyl group, anaryl group, substituted aryl group, a cyclic alkyl group, a substitutedcyclic alkyl group, a cyclic aralkyl group, a substituted cyclic aralkylgroup or multiple ring system, often having up to 20 carbon atoms. Inmany embodiments, R⁴ and R⁵ have between 3 and 10 carbon atoms, or are aC₁ to C₂₀ hydrocarbon group, a C₁ to C₂₀ aryl group or a C₁ to C₂₀aralkyl group, or a heteroatom containing group. R⁴ and R⁵ may beinterconnected to each other. R⁶ and R⁷ are independently absent,hydrogen, an alkyl group, halogen, heteroatom, or a hydrocarbyl group,such as a linear, cyclic, or branched alkyl group having 1 to 20 carbonatoms. In many embodiments, R⁶ and R⁷ are absent. R* may be absent, ormay be a hydrogen, a Group 14 atom containing group, a halogen, or aheteroatom containing group.

By “formal charge of the YZL or YZL′ ligand,” it is meant the charge ofthe entire ligand absent the metal and the leaving groups X. By “R¹ andR² may also be interconnected” it is meant that R¹ and R² may bedirectly bound to each other or may be bound to each other through othergroups. By “R⁴ and R⁵ may also be interconnected” it is meant that R⁴and R⁵ may be directly bound to each other or may be bound to each otherthrough other groups. An alkyl group may be linear, branched alkylradicals, alkenyl radicals, alkynyl radicals, cycloalkyl radicals, arylradicals, acyl radicals, aroyl radicals, alkoxy radicals, aryloxyradicals, alkylthio radicals, dialkylamino radicals, alkoxycarbonylradicals, aryloxycarbonyl radicals, carbomoyl radicals, alkyl- ordialkyl-carbamoyl radicals, acyloxy radicals, acylamino radicals,aroylamino radicals, straight, branched or cyclic, alkylene radicals, orcombination thereof. An aralkyl group is defined to be a substitutedaryl group.

In one or more embodiments, R⁴ and R⁵ are independently a grouprepresented by the following formula (VIII).

When R⁴ and R⁵ are as formula VII, R⁸ to R¹² are each independentlyhydrogen, a C₁ to C₄₀ alkyl group, a halide, a heteroatom, a heteroatomcontaining group containing up to 40 carbon atoms. In many embodiments,R⁸ to R¹² are a C₁ to C₂₀ linear or branched alkyl group, such as amethyl, ethyl, propyl, or butyl group. Any two of the R groups may forma cyclic group and/or a heterocyclic group. The cyclic groups may bearomatic. In one embodiment R⁹, R¹⁰ and R¹² are independently a methyl,ethyl, propyl, or butyl group (including all isomers). In anotherembodiment, R⁹, R¹⁰ and R¹² are methyl groups, and R⁸ and R¹¹ arehydrogen.

In one or more embodiments, R⁴ and R⁵ are both a group represented bythe following formula (IX).

When R⁴ and R⁵ follow formula IX, M is a Group 4 metal, such aszirconium, titanium, or hafnium. In many embodiments, M is zirconium.Each of L, Y, and Z may be a nitrogen. Each of R¹ and R² may be—CH₂—CH₂—. R³ may be hydrogen, and R⁶ and R⁷ may be absent.

The Group 15 metal-containing catalyst compound can be represented bythe following formula (X).

In formula X, Ph represents phenyl.

Catalyst Slurry

The catalyst system may include a catalyst or catalyst component in aslurry, which may have an initial catalyst compound, and an addedsolution catalyst component that is added to the slurry. The initialcatalyst component slurry may have no catalysts. In this case, two ormore solution catalysts may be added to the slurry to cause each to besupported.

Any number of combinations of catalyst components may be used inembodiments. For example, the catalyst component slurry can include anactivator and a support, or a supported activator. Further, the slurrycan include a catalyst compound in addition to the activator and thesupport. As noted, the catalyst compound in the slurry may be supported.

The slurry may include one or more activators and supports, and one morecatalyst compounds. For example, the slurry may include two or moreactivators (such as alumoxane and a modified alumoxane) and a catalystcompound, or the slurry may include a supported activator and more thanone catalyst compounds. In one embodiment, the slurry includes asupport, an activator, and two catalyst compounds. In another embodimentthe slurry includes a support, an activator and two different catalystcompounds, which may be added to the slurry separately or incombination. The slurry, containing silica and alumoxane, may becontacted with a catalyst compound, allowed to react, and thereafter theslurry is contacted with another catalyst compound, for example, in atrim system.

The molar ratio of metal in the activator to metal in the pre-catalystcompound in the slurry may be may be 1000:1 to 0.5:1, 300:1 to 1:1, or150:1 to 1:1. The slurry can include a support material which may be anyinert particulate carrier material known in the art, including, but notlimited to, silica, fumed silica, alumina, clay, talc or other supportmaterials such as disclosed above. In one embodiment, the slurrycontains silica and an activator, such as methyl aluminoxane (“MAO”),modified methyl aluminoxane (“MMAO”), as discussed further below.

One or more diluents or carriers can be used to facilitate thecombination of any two or more components of the catalyst system in theslurry or in the trim catalyst solution. For example, the single sitecatalyst compound and the activator can be combined together in thepresence of toluene or another non-reactive hydrocarbon or hydrocarbonmixture to provide the catalyst mixture. In addition to toluene, othersuitable diluents can include, but are not limited to, ethylbenzene,xylene, pentane, hexane, heptane, octane, other hydrocarbons, or anycombination thereof. The support, either dry or mixed with toluene canthen be added to the catalyst mixture or the catalyst/activator mixturecan be added to the support.

Catalyst Supports

As used herein, the terms “support” and “carrier” are usedinterchangeably and refer to any support material, including a poroussupport material, such as talc, inorganic oxides, and inorganicchlorides. The one or more single site catalyst compounds of the slurrycan be supported on the same or separate supports together with theactivator, or the activator can be used in an unsupported form, or canbe deposited on a support different from the single site catalystcompounds, or any combination thereof. This may be accomplished by anytechnique commonly used in the art. There are various other methods inthe art for supporting a single site catalyst compound. For example, thesingle site catalyst compound can contain a polymer bound ligand. Thesingle site catalyst compounds of the slurry can be spray dried. Thesupport used with the single site catalyst compound can befunctionalized.

The support can be or include one or more inorganic oxides, for example,of Group 2, 3, 4, 5, 13, or 14 elements. The inorganic oxide caninclude, but is not limited to silica, alumina, titania, zirconia,boria, zinc oxide, magnesia, or any combination thereof. Illustrativecombinations of inorganic oxides can include, but are not limited to,alumina-silica, silica-titania, alumina-silica-titania,alumina-zirconia, alumina-titania, and the like. The support can be orinclude alumina, silica, or a combination thereof. In one embodimentdescribed herein, the support is silica.

Suitable commercially available silica supports can include, but are notlimited to, ES757, ES70, and ES70W available from PQ Corporation.Suitable commercially available silica-alumina supports can include, butare not limited to, SIRAL® 1, SIRAL® 5, SIRAL® 10, SIRAL® 20, SIRAL®28M, SIRAL® 30, and SIRAL® 40, available from SASOL®. Generally,catalysts supports comprising silica gels with activators, such asmethylaluminoxanes (MAOs), are used in the trim systems described, sincethese supports may function better for co-supporting solution carriedcatalysts. Suitable supports may also be selected from the Cab-o-sil®materials available from Cabot Corporation and silica materialsavailable from the Grace division of W.R. Grace & Company.

Catalyst supports may also include polymers that are covalently bondedto a ligand on the catalyst. For example, two or more catalyst moleculesmay be bonded to a single polyolefin chain.

Catalyst Activators

As used herein, the term “activator” may refer to any compound orcombination of compounds, supported, or unsupported, which can activatea single site catalyst compound or component, such as by creating acationic species of the catalyst component. For example, this caninclude the abstraction of at least one leaving group (the “X” group inthe single site catalyst compounds described herein) from the metalcenter of the single site catalyst compound/component. The activator mayalso be referred to as a “co-catalyst”.

For example, the activator can include a Lewis acid or anon-coordinating ionic activator or ionizing activator, or any othercompound including Lewis bases, aluminum alkyls, and/orconventional-type co-catalysts. In addition to methylaluminoxane (“MAO”)and modified methylaluminoxane (“MMAO”) mentioned above, illustrativeactivators can include, but are not limited to, aluminoxane or modifiedaluminoxane, and/or ionizing compounds, neutral or ionic, such asDimethylanilinium tetrakis(pentafluorophenyl)borate, Triphenylcarbeniumtetrakis(pentafluorophenyl)borate, Dimethylaniliniumtetrakis(3,5-(CF₃)₂phenyl)borate, Triphenylcarbeniumtetrakis(3,5-(CF₃)₂phenyl)borate, Dimethylaniliniumtetrakis(perfluoronapthyl)borate, Triphenylcarbeniumtetrakis(perfluoronapthyl)borate, Dimethylaniliniumtetrakis(pentafluorophenyl)aluminate, Triphenylcarbeniumtetrakis(pentafluorophenyl)aluminate, Dimethylaniliniumtetrakis(perfluoronapthyl)aluminate, Triphenylcarbeniumtetrakis(perfluoronapthyl)aluminate, a tris(perfluorophenyl)boron, atris(perfluoronaphthyl)boron, tris(perfluorophenyl)aluminum, atris(perfluoronaphthyl)aluminum or any combinations thereof.

It is recognized that these activators may or may not bind directly tothe support surface or may be modified to allow them to be bound to asupport surface while still maintaining their compatability with thepolymerization system. Such tethering agents may be derived from groupsthat are reactive with surface hydroxyl species. Non-limiting examplesof reactive functional groups that can be used to create tethers includealuminum halides, aluminum hydrides, aluminum alkyls, aluminum aryls,sluminum alkoxides, electrophilic silicon reagents, alkoxy silanes,amino silanes, boranes.

Aluminoxanes can be described as oligomeric aluminum compounds having—Al(R)—O-subunits, where R is an alkyl group. Examples of aluminoxanesinclude, but are not limited to, methylaluminoxane (“MAO”), modifiedmethylaluminoxane (“MMAO”), ethylaluminoxane, isobutylaluminoxane, or acombination thereof. Aluminoxanes can be produced by the hydrolysis ofthe respective trialkylaluminum compound. MMAO can be produced by thehydrolysis of trimethylaluminum and a higher trialkylaluminum, such astriisobutylaluminum. MMAOs are generally more soluble in aliphaticsolvents and more stable during storage. There are a variety of methodsfor preparing aluminoxane and modified aluminoxanes.

In one or more embodiments, a visually clear MAO can be used. Forexample, a cloudy or gelled aluminoxane can be filtered to produce aclear aluminoxane or clear aluminoxane can be decanted from a cloudyaluminoxane solution. In another embodiment, a cloudy and/or gelledaluminoxane can be used. Another aluminoxane can include a modifiedmethyl aluminoxane (“MMAO”) type 3A (commercially available from AkzoChemicals, Inc. under the trade name Modified Methylaluminoxane type 3A,discussed and described in U.S. Pat. No. 5,041,584). A suitable sourceof MAO can be a solution having from about 1 wt. % to about a 50 wt. %MAO, for example. Commercially available MAO solutions can include the10 wt. % and 30 wt. % MAO solutions available from AlbemarleCorporation, of Baton Rouge, La.

As noted above, one or more organo-aluminum compounds such as one ormore alkylaluminum compounds can be used in conjunction with thealuminoxanes. For example, alkylaluminum species that may be used arediethylaluminum ethoxide, diethylaluminum chloride, and/ordiisobutylaluminum hydride. Examples of trialkylaluminum compoundsinclude, but are not limited to, trimethylaluminum, triethylaluminum(“TEAL”), triisobutylaluminum (“TiBA1”), tri-n-hexylaluminum,tri-n-octylaluminum, tripropylaluminum, tributylaluminum, and the like.

Catalyst Component Solutions

The catalyst component solution may include only a catalyst compound ormay include an activator in addition to the catalyst compound. Thecatalyst solution used in the trim process can be prepared by dissolvingthe catalyst compound and optional activators in a liquid solvent. Theliquid solvent may be an alkane, such as a C₅ to C₃₀ alkane, or a C₅ toC₁₀ alkane. Cyclic alkanes such as cyclohexane and aromatic compoundssuch as toluene may also be used. In addition, mineral oil may be usedas a solvent. The solution employed should be liquid under theconditions of polymerization and relatively inert. In one embodiment,the liquid utilized in the catalyst compound solution is different fromthe diluent used in the catalyst component slurry. In anotherembodiment, the liquid utilized in the catalyst compound solution is thesame as the diluent used in the catalyst component solution.

If the catalyst solution includes both activator and catalyst compound,the ratio of metal in the activator to metal in the pre-catalystcompound in the solution may be may be 1000:1 to 0.5:1, 300:1 to 1:1, or150:1 to 1:1. In certain cases, it may be advantageous to have an excessof catalyst compound such that the ratio is <1:1, for example, 1:1 to0.5:1 or 1:1 to 0.1:1 or 1:1 to 0.01. In various embodiments, theactivator and catalyst compound is present in the solution at up toabout 90 wt. %, at up to about 50 wt. %, at up to about 20 wt. %,preferably at up to about 10 wt. %, at up to about 5 wt. %, at less than1 wt. %, or between 100 ppm and 1 wt. %, based upon the weight of thesolvent and the activator or catalyst compound.

The catalyst component solution can comprise any one of the solublecatalyst compounds described in the catalyst section herein. As thecatalyst is dissolved in the solution, a higher solubility is desirable.Accordingly, the catalyst compound in the catalyst component solutionmay often include a metallocene, which may have higher solubility thanother catalysts.

In the polymerization process, described below, any of the abovedescribed catalyst component containing solutions may be combined withany of the catalyst component containing slurry/slurries describedabove. In addition, more than one catalyst component solution may beutilized.

Continuity Additive/Static Control Agents

In gas-phase polyethylene production processes, as disclosed herein, itmay be desirable to additionally use one or more static control agentsto aid in regulating static levels in the reactor. As used herein, astatic control agent is a chemical composition which, when introducedinto a fluidized bed reactor, may influence or drive the static charge(negatively, positively, or to zero) in the fluidized bed. The specificstatic control agent used may depend upon the nature of the staticcharge, and the choice of static control agent may vary dependent uponthe polymer being produced and the single site catalyst compounds beingused.

Control agents such as aluminum stearate may be employed. The staticcontrol agent used may be selected for its ability to receive the staticcharge in the fluidized bed without adversely affecting productivity.Other suitable static control agents may also include aluminumdistearate, ethoxlated amines, and anti-static compositions such asthose provided by Innospec Inc. under the trade name OCTASTAT. Forexample, OCTASTAT 2000 is a mixture of a polysulfone copolymer, apolymeric polyamine, and oil-soluble sulfonic acid.

Any of the aforementioned control agent may be employed either alone orin combination as a control agent. For example, the carboxylate metalsalt may be combined with an amine containing control agent (e.g., acarboxylate metal salt with any family member belonging to the KEMAMINE®(available from Crompton Corporation) or ATMER® (available from ICIAmericas Inc.) family of products).

Other useful continuity additives include ethyleneimine additives usefulin embodiments disclosed herein may include polyethyleneimines havingthe following general formula:

—(CH₂—CH₂—NH)_(n)—

in which n may be from about 10 to about 10,000. The polyethyleneiminesmay be linear, branched, or hyperbranched (e.g., forming dendritic orarborescent polymer structures). They can be a homopolymer or copolymerof ethyleneimine or mixtures thereof (referred to aspolyethyleneimine(s) hereafter). Although linear polymers represented bythe chemical formula —[CH₂—CH₂—NH]— may be used as thepolyethyleneimine, materials having primary, secondary, and tertiarybranches can also be used. Commercial polyethyleneimine can be acompound having branches of the ethyleneimine polymer. Suitablepolyethyleneimines are commercially available from BASF Corporationunder the trade name Lupasol. These compounds can be prepared as a widerange of molecular weights and product activities. Examples ofcommercial polyethyleneimines sold by BASF suitable for use in thepresent invention include, but are not limited to, Lupasol FG andLupasol WF. Another useful continuity additive can include a mixture ofaluminum distearate and an ethoxylated amine-type compound, e.g.,IRGASTAT AS-990, available from Huntsman (formerly Ciba SpecialtyChemicals). The mixture of aluminum distearate and ethoxylated aminetype compound can be slurried in mineral oil e.g., Hydrobrite 380. Forexample, the mixture of aluminum distearate and an ethoxylated aminetype compound can be slurried in mineral oil to have total slurryconcentration of ranging from about 5 wt. % to about 50 wt. % or about10 wt. % to about 40 wt. %, or about 15 wt. % to about 30 wt. %. Otheruseful static control agents and additives are disclosed in U.S. PatentApplication Publication No. 2008/0045663.

The continuity additive(s) or static control agent(s) may be added tothe reactor in an amount ranging from 0.05 to 200 ppm, based on theweight of all feeds to the reactor, excluding recycle. In someembodiments, the continuity additive may be added in an amount rangingfrom 2 to 100 ppm, or in an amount ranging from 4 to 50 ppm.

Gas Phase Polymerization Reactor

FIG. 1 is a schematic of a gas-phase reactor system 100, showing theaddition of at least two catalysts, at least one of which is added as atrim catalyst. The catalyst component slurry, preferably a mineral oilslurry including at least one support and at least one activator, atleast one supported activator, and optional catalyst compounds may beplaced in a vessel or catalyst pot (cat pot) 102. In one embodiment, thecat pot 102 is an agitated holding tank designed to keep the solidsconcentration homogenous. A catalyst component solution, prepared bymixing a solvent and at least one catalyst compound and/or activator, isplaced in another vessel, which can be termed a trim pot 104. Thecatalyst component slurry can then be combined in-line with the catalystcomponent solution to form a final catalyst composition. A nucleatingagent 106, such as silica, alumina, fumed silica or any otherparticulate matter may be added to the slurry and/or the solutionin-line or in the vessels 102 or 104. Similarly, additional activatorsor catalyst compounds may be added in-line. For example, a secondcatalyst slurry that includes a different catalyst may be introducedfrom a second cat pot. The two catalyst slurries may be used as thecatalyst system with or without the addition of a solution catalyst fromthe trim pot.

The catalyst component slurry and solution can be mixed in-line. Forexample, the solution and slurry may be mixed by utilizing a staticmixer 108 or an agitating vessel (not shown). The mixing of the catalystcomponent slurry and the catalyst component solution should be longenough to allow the catalyst compound in the catalyst component solutionto disperse in the catalyst component slurry such that the catalystcomponent, originally in the solution, migrates to the supportedactivator originally present in the slurry. The combination forms auniform dispersion of catalyst compounds on the supported activatorforming the catalyst composition. The length of time that the slurry andthe solution are contacted is typically up to about 120 minutes, such asabout 0.01 to about 60 minutes, about 5 to about 40 minutes, or about 10to about 30 minutes.

When combining the catalysts, the activator and the optional support oradditional cocatalysts, in the hydrocarbon solvents immediately prior toa polymerization reactor it is desirable that the combination yield anew polymerization catalyst in less than 1 h, less than 30 min, or lessthan 15 min. Shorter times are more effective, as the new catalyst isready before being introduces into the reactor, providing the potentialfor faster flow rates.

In another embodiment, an aluminum alkyl, an ethoxylated aluminum alkyl,an aluminoxane, an anti-static agent or a borate activator, such as a C₁to C₁₅ alkyl aluminum (for example tri-isobutyl aluminum, trimethylaluminum or the like), a C₁ to C₁₅ ethoxylated alkyl aluminum or methylaluminoxane, ethyl aluminoxane, isobutylaluminoxane, modifiedaluminoxane or the like are added to the mixture of the slurry and thesolution in line. The alkyls, antistatic agents, borate activatorsand/or aluminoxanes may be added from an alkyl vessel 110 directly tothe combination of the solution and the slurry, or may be added via anadditional alkane (such as isopentane, hexane, heptane, and or octane)carrier stream, for example, from a hydrocarbon vessel 112. Theadditional alkyls, antistatic agents, borate activators and/oraluminoxanes may be present at up to about 500 ppm, at about 1 to about300 ppm, at 10 to about 300 ppm, or at about 10 to about 100 ppm.Carrier streams that may be used include isopentane and or hexane, amongothers. The carrier may be added to the mixture of the slurry and thesolution, typically at a rate of about 0.5 to about 60 lbs/hr (27 kg/hr)or greater, depending on reactor size. Likewise a carrier gas 114, suchas nitrogen, argon, ethane, propane and the like, may be added in-lineto the mixture of the slurry and the solution. Typically the carrier gasmay be added at the rate of about 1 to about 100 lb/hr (0.4 to 45kg/hr), or about 1 to about 50 lb/hr (5 to 23 kg/hr), or about 1 toabout 25 lb/hr (0.4 to 11 kg/hr).

In another embodiment, a liquid carrier stream is introduced into thecombination of the solution and slurry that is moving in a downwarddirection. The mixture of the solution, the slurry and the liquidcarrier stream may pass through a mixer or length of tube for mixingbefore being contacted with a gaseous carrier stream.

Similarly, a comonomer 116, such as hexene, another alpha-olefin ordiolefin, may be added in-line to the mixture of the slurry and thesolution. The slurry/solution mixture is then passed through aninjection tube 118 to a reactor 120. To assist in proper formation ofparticles in the reactor 120, a nucleating agent 122, such as fumedsilica, can be added directly into the reactor 120. In some embodiments,the injection tube may aerosolize the slurry/solution mixture. Anynumber of suitable tubing sizes and configurations may be used toaerosolize and/or inject the slurry/solution mixture. In one embodiment,a gas stream 124, such as cycle gas, or re-cycle gas 126, monomer,nitrogen, or other materials is introduced into a support tube 128 thatsurrounds the injection tube 118.

When a metallocene catalyst or other similar catalyst is used in the gasphase reactor, oxygen or fluorobenzene can be added to the reactor 120directly or to the gas stream 124 to control the polymerization rate.Thus, when a metallocene catalyst (which is sensitive to oxygen orfluorobenzene) is used in combination with another catalyst (that is notsensitive to oxygen) in a gas phase reactor, oxygen can be used tomodify the metallocene polymerization rate relative to thepolymerization rate of the other catalyst. An example of such a catalystcombination is bis(n-propyl cyclopentadienyl)zirconium dichloride and[(2,4,6-Me₃C₆H₂)NCH₂CH₂]₂NHZrBn₂, where Me is methyl orbis(indenyl)zirconium dichloride and [(2,4,6-Me₃C₆H₂)NCH₂CH₂]₂NHHfBn₂,where Me is methyl. For example, if the oxygen concentration in thenitrogen feed is altered from 0.1 ppm to 0.5 ppm, significantly lesspolymer from the bisindenyl ZrCl₂ will be produced and the relativeamount of polymer produced from the [(2,4,6-Me₃C₆H₂)NCH₂CH₂]₂NHHfBn₂ isincreased. In one embodiment, the contact temperature of the slurry andthe solution is in the range of from 0° C. to about 80° C., from about0° C. to about 60° C., from about 10° C., to about 50° C. and from about20° C. to about 40° C.

The example above is not limiting, as additional solutions and slurriesmay be included. For example, a slurry can be combined with two or moresolutions having the same or different catalyst compounds and oractivators. Likewise, the solution may be combined with two or moreslurries each having the same or different supports, and the same ordifferent catalyst compounds and or activators. Similarly, two or moreslurries combined with two or more solutions, preferably in-line, wherethe slurries each comprise the same or different supports and maycomprise the same or different catalyst compounds and or activators andthe solutions comprise the same or different catalyst compounds and oractivators. For example, the slurry may contain a supported activatorand two different catalyst compounds, and two solutions, each containingone of the catalysts in the slurry, are each independently combined,in-line, with the slurry.

Use of Catalyst Composition to Control Product Properties

The properties of the product polymer may be controlled by adjusting thetiming, temperature, concentrations, and sequence of the mixing of thesolution, the slurry and any optional added materials (nucleatingagents, catalyst compounds, activators, etc) described above. The MWD,composition distribution, melt index, relative amount of polymerproduced by each catalyst, and other properties of the polymer producedmay also be changed by manipulating process parameters. Any number ofprocess parameters may be adjusted, including manipulating hydrogenconcentration in the polymerization system, changing the amount of thefirst catalyst in the polymerization system, changing the amount of thesecond catalyst in the polymerization system. Other process parametersthat can be adjusted include changing the relative ratio of the catalystin the polymerization process (and optionally adjusting their individualfeed rates to maintain a steady or constant resin production rate). Theconcentrations of reactants in the reactor 120 can be adjusted bychanging the amount of liquid or gas that is withdrawn or purged fromthe process, changing the amount and/or composition of a recoveredliquid and/or recovered gas returned to the polymerization process,wherein the recovered liquid or recovered gas can be recovered frompolymer discharged from the polymerization process. Furtherconcentration parameters that can be adjusted include changing thepolymerization temperature, changing the ethylene partial pressure inthe polymerization process, changing the ethylene to comonomer ratio inthe polymerization process, changing the activator to transition metalratio in the activation sequence. Time dependant parameters may beadjusted, such as changing the relative feed rates of the slurry orsolution, changing the mixing time, the temperature and or degree ofmixing of the slurry and the solution in-line, adding different types ofactivator compounds to the polymerization process, and adding oxygen orfluorobenzene or other catalyst poison to the polymerization process.Any combinations of these adjustments may be used to control theproperties of the final polymer product.

In one embodiment, the composition distribution of the polymer productis measured at regular intervals and one of the above processparameters, such as temperature, catalyst compound feed rate, the ratioof the two or more catalysts to each other, the ratio of comonomer tomonomer, the monomer partial pressure, and or hydrogen concentration, isaltered to bring the composition to the desired level, if necessary. Thecomposition distribution may be performed by temperature rising elutionfractionation (TREF), or similar techniques TREF measures composition asa function of elution temperature.

In one embodiment, a polymer product property is measured in-line and inresponse the ratio of the catalysts being combined is altered. In oneembodiment, the molar ratio of the catalyst compound in the catalystcomponent slurry to the catalyst compound in the catalyst componentsolution, after the slurry and solution have been mixed to form thefinal catalyst composition, is 500:1 to 1:500, or 100:1 to 1:100, or50:1 to 1:50, or 10:1 to 1:10, or 5:1 to 1:5. In another embodiment, themolar ratio of a Group 15 catalyst compound in the slurry to a ligandmetallocene catalyst compound in the solution, after the slurry andsolution have been mixed to form the catalyst composition, is 500:1,100:1, 50:1, 10:1, 5:1, 1:5, 1:10, 1:100, or 1:500. The product propertymeasured can include the polymer product's flow index, melt index,density, MWD, comonomer content, composition distribution, andcombinations thereof. In another embodiment, when the ratio of thecatalyst compounds is altered, the introduction rate of the catalystcomposition to the reactor, or other process parameters, is altered tomaintain a desired production rate.

While not wishing to be bound by or limited to any theory, it isbelieved that the processes described herein immobilize the solutioncatalyst compound in and on a support, preferably a supported activator.The in-line immobilization techniques described herein preferably resultin a supported catalyst system that when introduced to the reactorprovides for suitable polymer properties, with appropriate particlemorphology, bulk density, or higher catalyst activities and without theneed for additional equipment in order to introduce catalyst compoundsolution into a reactor, particularly a gas phase or slurry phasereactor.

Polymerization Process

The catalyst system can be used to polymerize one or more olefins toprovide one or more polymer products therefrom. Any suitablepolymerization process can be used, including, but not limited to, highpressure, solution, slurry, and/or gas phase polymerization processes.In embodiments that use other techniques besides gas phasepolymerization, modifications to a catalyst addition system that aresimilar to those discussed with respect to FIG. 1 can be used. Forexample, a trim system may be used to feed catalyst to a loop slurryreactor for polyethylene copolymer production.

The terms “polyethylene” and “polyethylene copolymer” refer to a polymerhaving at least 50 wt. % ethylene-derived units. In various embodiments,the polyethylene can have at least 70 wt. % ethylene-derived units, atleast 80 wt. % ethylene-derived units, at least 90 wt. %ethylene-derived units, at least 95 wt. % ethylene-derived units, or 100wt. % ethylene-derived units. The polyethylene can, thus, be ahomopolymer or a copolymer, including a terpolymer, having one or moreother monomeric units. As described herein, a polyethylene can include,for example, at least one or more other olefins or comonomers. Suitablecomonomers can contain 3 to 16 carbon atoms, from 3 to 12 carbon atoms,from 4 to 10 carbon atoms, and from 4 to 8 carbon atoms. Examples ofcomonomers include, but are not limited to, propylene, 1-butene,1-pentene, 1-hexene, 1-heptene, 1-octene, 4-methylpent-1-ene, 1-decene,1-dodecene, 1-hexadecene, and the like. Additionally, small amounts ofdiene monomers, such as 1,7-octadiene may be added to the polymerizationto adjust polymer properties.

Referring again to FIG. 1, the fluidized bed reactor 120 can include areaction zone 130 and a velocity reduction zone 132. The reaction zone130 can include a bed 134 that includes growing polymer particles,formed polymer particles and a minor amount of catalyst particlesfluidized by the continuous flow of the gaseous monomer and diluent toremove heat of polymerization through the reaction zone. Optionally,some of the re-circulated gases 124 can be cooled and compressed to formliquids that increase the heat removal capacity of the circulating gasstream when readmitted to the reaction zone. A suitable rate of gas flowcan be readily determined by experimentation. Make-up of gaseous monomerto the circulating gas stream can be at a rate equal to the rate atwhich particulate polymer product and monomer associated therewith iswithdrawn from the reactor and the composition of the gas passingthrough the reactor can be adjusted to maintain an essentially steadystate gaseous composition within the reaction zone. The gas leaving thereaction zone 130 can be passed to the velocity reduction zone 132 whereentrained particles are removed, for example, by slowing and fallingback to the reaction zone 130. If desired, finer entrained particles anddust can be removed in a separation system 136, such as a cyclone and/orfines filter. The gas 124 can be passed through a heat exchanger 138where at least a portion of the heat of polymerization can be removed.The gas can then be compressed in a compressor 140 and returned to thereaction zone 130.

The reactor temperature of the fluid bed process can be greater thanabout 30° C., about 40° C., about 50° C., about 90° C., about 100° C.,about 110° C., about 120° C., about 150° C., or higher. In general, thereactor temperature is operated at the highest feasible temperaturetaking into account the sintering temperature of the polymer productwithin the reactor. Preferred reactor temperatures are between 70 and95° C. More preferred reactor temperatures are between 75 and 90° C.Thus, the upper temperature limit in one embodiment is the meltingtemperature of the polyethylene copolymer produced in the reactor.However, higher temperatures may result in narrower MWDs, which can beimproved by the addition of the MCN, or other, co-catalysts, asdescribed herein.

Hydrogen gas can be used in olefin polymerization to control the finalproperties of the polyolefin. Using certain catalyst systems, increasingconcentrations (partial pressures) of hydrogen can increase the flowindex (FI) of the polyethylene copolymer generated. The flow index canthus be influenced by the hydrogen concentration. The amount of hydrogenin the polymerization can be expressed as a mole ratio relative to thetotal polymerizable monomer, for example, ethylene, or a blend ofethylene and hexene or propylene.

The amount of hydrogen used in the polymerization process can be anamount necessary to achieve the desired flow index of the finalpolyolefin resin. For example, the mole ratio of hydrogen to totalmonomer (H₂:monomer) can be greater than about 0.0001, greater thanabout 0.0005, or greater than about 0.001. Further, the mole ratio ofhydrogen to total monomer (H₂:monomer) can be less than about 10, lessthan about 5, less than about 3, and less than about 0.10. A desirablerange for the mole ratio of hydrogen to monomer can include anycombination of any upper mole ratio limit with any lower mole ratiolimit described herein. Expressed another way, the amount of hydrogen inthe reactor at any time can range to up to about 5,000 ppm, up to about4,000 ppm in another embodiment, up to about 3,000 ppm, or between about50 ppm and 5,000 ppm, or between about 50 ppm and 2,000 ppm in anotherembodiment. The amount of hydrogen in the reactor can range from a lowof about 1 ppm, about 50 ppm, or about 100 ppm to a high of about 400ppm, about 800 ppm, about 1,000 ppm, about 1,500 ppm, or about 2,000ppm. Further, the ratio of hydrogen to total monomer (H₂:monomer) can beabout 0.00001:1 to about 2:1, about 0.005:1 to about 1.5:1, or about0.0001:1 to about 1:1. The one or more reactor pressures in a gas phaseprocess (either single stage or two or more stages) can vary from 690kPa (100 psig) to 3,448 kPa (500 psig), in the range from 1,379 kPa (200psig) to 2,759 kPa (400 psig), or in the range from 1,724 kPa (250 psig)to 2,414 kPa (350 psig).

The gas phase reactor can be capable of producing from about 10 kg ofpolymer per hour (25 lbs/hr) to about 90,900 kg/hr (200,000 lbs/hr), orgreater, and greater than about 455 kg/hr (1,000 lbs/hr), greater thanabout 4,540 kg/hr (10,000 lbs/hr), greater than about 11,300 kg/hr(25,000 lbs/hr), greater than about 15,900 kg/hr (35,000 lbs/hr), andgreater than about 22,700 kg/hr (50,000 lbs/hr), and from about 29,000kg/hr (65,000 lbs/hr) to about 45,500 kg/hr (100,000 lbs/hr).

As noted, a slurry polymerization process can also be used inembodiments. A slurry polymerization process generally uses pressures inthe range of from about 101 kPa (1 atmosphere) to about 5,070 kPa (50atmospheres) or greater, and temperatures in the range of from about 0°C. to about 120° C., and more particularly from about 30° C. to about100° C. In a slurry polymerization, a suspension of solid, particulatepolymer can be formed in a liquid polymerization diluent medium to whichethylene, comonomers, and hydrogen along with catalyst can be added. Thesuspension including diluent can be intermittently or continuouslyremoved from the reactor where the volatile components are separatedfrom the polymer and recycled, optionally after a distillation, to thereactor. The liquid diluent employed in the polymerization medium can bean alkane having from 3 to 7 carbon atoms, such as, for example, abranched alkane. The medium employed should be liquid under theconditions of polymerization and relatively inert. When a propane mediumis used the process should be operated above the reaction diluentcritical temperature and pressure. In one embodiment, a hexane,isopentane, or isobutane medium can be employed. The slurry can becirculated in a continuous loop system.

The product polyethylene can have a melt index ratio (MIR or I₂₁/I₂)ranging from about 5 to about 300, or from about 10 to less than about150, or, in many embodiments, from about 15 to about 50. Flow index (FI,HLMI, or I₂₁ can be measured in accordance with ASTM D1238 (190° C.,21.6 kg). The melt index (MI, I₂) can be measured in accordance withASTM D1238 (at 190° C., 2.16 kg weight).

Density can be determined in accordance with ASTM D-792. Density isexpressed as grams per cubic centimeter (g/cm³) unless otherwise noted.The polyethylene can have a density ranging from a low of about 0.89g/cm³, about 0.90 g/cm³, or about 0.91 g/cm³ to a high of about 0.95g/cm³, about 0.96 g/cm³, or about 0.97 g/cm³. The polyethylene can havea bulk density, measured in accordance with ASTM D1895 method B, of fromabout 0.25 g/cm³ to about 0.5 g/cm³. For example, the bulk density ofthe polyethylene can range from a low of about 0.30 g/cm³, about 0.32g/cm³, or about 0.33 g/cm³ to a high of about 0.40 g/cm³, about 0.44g/cm³, or about 0.48 g/cm³.

The polyethylene can be suitable for such articles as films, fibers,nonwoven and/or woven fabrics, extruded articles, and/or moldedarticles. Examples of films include blown or cast films formed bycoextrusion or by lamination useful as shrink film, cling film, stretchfilm, sealing films, oriented films, snack packaging, heavy duty bags,grocery sacks, baked and frozen food packaging, medical packaging,industrial liners, membranes, etc. in food-contact and non-food contactapplications, agricultural films and sheets. Examples of fibers includemelt spinning, solution spinning and melt blown fiber operations for usein woven or non-woven form to make filters, diaper fabrics, hygieneproducts, medical garments, geotextiles, etc. Examples of extrudedarticles include tubing, medical tubing, wire and cable coatings, pipe,geomembranes, and pond liners. Examples of molded articles includesingle and multi-layered constructions in the form of bottles, tanks,large hollow articles, rigid food containers and toys, etc.

Examples

To provide a better understanding of the foregoing discussion, thefollowing non-limiting examples are provided. All parts, proportions,and percentages are by weight unless otherwise indicated.

As described herein, comonomer, such as a C₄-C₈ alpha-olefin is added toa reaction, along with ethylene monomer, to create short chain branching(SCB) in polyethylene copolymers. Without intending to be being limitedby theory, the SCB may cause a long PE chain to break free from acrystallite and be partly incorporated into other crystallites.Accordingly, polymers that have SCB on longer chains may exhibit highertoughness.

In contrast, long chain branching (LCB) are points at which two polymerchains may divide off from single polymer chains. LCB may enhancetoughness, but cause the polymer to more vulnerable to orientation,causing lower tear strength in the direction of extrusion.

The inclusion of shorter chains lowers the melt temperature of thepolymer, and may enhance the processability. However, SCB on shorterchains may force these chains out of crystallites and into amorphousregions, lowering the toughness of the resulting polymer product.

Hydrogen may be added to the polymer reactions to control molecularweight. The hydrogen acts as chain termination agent, essentiallyreplacing a monomer or comonomer molecule in the reaction. This stopsthe formation of a current polymer chain, and allows a new polymer chainto begin.

Catalyst System Comonomer Incorporation Versus MWD Control, Results fromSix Inch Gas Phase Reactor

Polymerization Experiments in 6 Inch Diameter Gas-Phase Reactor

The catalysts A-J shown in Table 1 were prepared as discussed below. Allthe catalysts prepared were screened in a fluidized bed reactor equippedwith devices for temperature control, catalyst feeding or injectionequipment, gas chromatograph (GC) analyzer for monitoring andcontrolling monomer and comonomer gas feeds and equipment for polymersampling and collecting. The reactor consisted of a 6 inch (15.24 cm)diameter bed section increasing to 10 inches (25.4 cm) at the reactortop. Gas comes in through a perforated distributor plate allowingfluidization of the bed contents and polymer sample is discharged at thereactor top. The comonomer in the example polymerizations herein is1-hexene. The polymerization parameters are outlined in the table 1below and plotted in FIGS. 2 and 3.

The reacting bed of growing polymer particles was maintained in afluidized state by continually flowing the makeup feed and recycle gasthrough the reaction zone at a superficial gas velocity 1-2 ft/sec (0.3to 0.6 m/sec). The reactor was operated at a temperature of 175 F (79 C)and total pressure of 300 psig (2274 kPa gauge) including 35 mol %ethylene.

TABLE 1 Polymerization Experiments in 6 Inch Diameter Gas-Phase ReactorC6/C2 Feed ratio [H2]/C2 C6/C2 Density MI = I2 MIR Metallocene (g/g)(ppm/mol %) (mol/mol) (g/mL) (g/10 min) (I21/I2) A (CpMe₅)(1-MeInd)ZrCl₂0.096 0.4 0.038 0.928 1.84 18.5 B (1-EtInd)₂ZrCl₂ 0.115 0.7 0.036 0.9232.58 17.2 C (Me₄Cp)₁-MeIndZrCl₂ 0.104 0.7 0.036 0.922 1.05 20.5 D(1-MeInd)₂ZrCl₂ 0.132 1.2 0.044 0.92 1.62 18.3 E(Me₄Cp)(1,3-Me₂Ind)ZrCl₂ 0.151 1.7 0.07 0.921 1.19 20.1 F (1-Bu,3-MeCp)ZrCl₂ 0.086 3.3 0.019 0.917 1.1 17.4 G (Me₄PrCp)MeCpZrCl₂ 0.0943.4 0.031 0.918 1.1 18.5 H (Me₄Cp)PrCpZrCl₂ 0.083 3.0 0.022 0.919 0.9518.6 I (PrCp)₂HfF₂ 0.078 4.8 0.009 0.917 0.79 21.8 J(CH2)₃Si(CpMe₄)CpZrCl₂ 0.083 23.4 0.011 0.92 0.66 90.3

FIG. 2 is a plot 200 of a series of polymers that were prepared to testthe relative abilities of a series of metallocene catalysts to prepare aresin having about a 1 melt index (MI) and a density (D) of about 0.92.The polymerizations were performed in the continuous gas phase reactor(LGPR) described above. The left axis 202 represents the gas-phaseratios of hydrogen to ethylene monomer (H₂/C₂) used to achieve thetarget properties, in units of parts-per-million (mol) of H₂ per mol %C₂ (ppm/mol %). The right axis 204 represents the comonomer to ethyleneratio (C₆/C₂) used to achieve the target properties, in units of mol permol.

Comparing C₆/C₂ levels used to achieve the property targets indicate therelative abilities of the catalysts to incorporate comonomer. Forexample, comparing the C₆/C₂ level 206 for (1-EtInd)₂ZrCl₂ (B) to theC₆/C₂ level 208 for (PrCp)₂HfF₂ (I) gives a ratio of about 36/9 or aboutfour. This indicates that for a given C₆/C₂ gas ratio, a polymerprepared with (PrCp)₂HfF₂ will have approximately four times the shortchain branching (SCB) of a polymer prepared using (1-EtInd)₂ZrCl₂. Thisdata is useful for controlling composition distributions of polymersmade as in-situ blends using catalyst mixtures, for example, asco-supported catalysts on a single support. The data is also useful fordetermining which catalysts should be combined to have a compositiondistribution containing both comonomer rich (low density) and comonomerpoor (high density) components.

The effects of the steady state gas ratios for H₂/C₂ (ppm/mol) 202 areshown by the bars. The levels of these bars roughly indicate therelative molecular weight capabilities of the catalysts. For example,(CH₂)₃Si(CpMe₄)CpZrCl₂ (J) requires a H₂/C₂ ratio 210 of about 23.4ppm/mol to achieve a target melt index of about one, and(CpMe₅)(1-MeInd)ZrCl₂ (A) requires a H₂/C₂ ratio 212 of about 0.4ppm/mol to achieve the same target melt index. These results indicatethat (CH₂)₃Si(CpMe₄)CpZrCl₂ (J) yields a higher Mw polymer than(CpMe₅)(1-MeInd)ZrCl₂ (A) at the same H₂/C₂ ratio. In this example, thedata is approximate since the change in Mw is not measured as a functionof H₂/C₂.

FIG. 3 is a plot 300 of the series of polymers of FIG. 2, showing themelt index ratio (MIR) of the series of polymers made by differentmetallocene (MCN) catalysts. As used herein, the terms melt index ratio(MIR), melt flow ratio (MFR), and “I₂₁/I₂,” interchangeably refer to theratio of the flow index (“FI” or “I₂₁”) to the melt index (“MI” or“I₂”). The MI (I₂) can be measured in accordance with ASTM D1238 (at190° C., 2.16 kg weight). The FI (I₂₁) can be measured in accordancewith ASTM D1238 (at 190° C., 21.6 kg weight). Like numbered items are asdescribed with respect to FIG. 2. In this plot 300, the left axis 302represents the MIR. The MIR (which may also be termed melt flow ratio orMFR) is the ratio of the I21 and I2 melt indices and may indicate thepresence of long chain branching. For linear resins, without LCB, theratio is around 25 or less. Higher MIR values may indicate the presenceof LCB which can be detrimental to film properties, as noted above. Thehighest MIR ratio 304 was for (CH₂)₃Si(CpMe₄)CpZrCl₂ (J), indicatingthat polymer produced by this catalyst has the most LCB. In contrast,blending resins for with the two different catalysts forms a finalproduct that will have a higher MIR.

Using the results shown in FIGS. 2 and 3, five catalysts were selectedto determine the dependence of the molecular weight (Mw) on the H₂ratio. These catalysts included three catalysts that generate lower Mwpolyethylene, (CpMe₅)(1-MeInd)ZrCl₂ (A) 306, (1-EtInd)₂ZrCl₂ (B) 308,and (Me₄Cp)(1,3-Me₂Ind)ZrCl₂ (E) 310. The catalysts also included acatalyst that generates a middle Mw polyethylene, (PrCp)₂HfF₂ (I) 312.Table 2 contains data on the dependence of Mw on H₂/C₂ level.

TABLE 2 Mw vs. H₂/C₂ level for selected MCNs Run No Catalyst H₂/C₂(ppm/mol) Mw Mw/Mn 1/Mw 1 (CpMe₅)1-MeIndZrCl₂ 0.2 186,862 3.275.3515E−06 2 (CpMe₅)1-MeIndZrCl₂ 4.3 60,228 4.65 1.6604E−05 3(CpMe₅)1-MeIndZrCl₂ 6.3 48,140 5.58 2.0773E−05 4 (1-EtInd)₂ZrCl₂ 0.5125,656 3.18 7.9582E−06 5 (1-EtInd)₂ZrCl₂ 4.2 47,275 4.34 2.1153E−05 6(Me₄Cp) (1,3-Me₂Ind)ZrCl₂ 0.3 167,546 4.31 5.9685E−06 7 (Me₄Cp)(1,3-Me₂Ind)ZrCl₂ 4.3 72,602 3.85 1.3774E−05 8 (PrCp)₂HfF₂ 2.0 193,0862.82 5.1790E−06 9 (PrCp)₂HfF₂ 4.8 132,536 2.81 7.5451E−06 10 (PrCp)₂HfF₂10.2 63,030 2.98 1.5865E−05

These results were used to generate a series of plots that can be usedto determine the sensitivity of the Mw to H₂/C₂ ratios. Table 3indicates the slope and intercepts of the reciprocal plots. The lower Mwcatalysts had larger slopes, indicating a greater influence of H₂/C₂ratios on Mw. The second catalyst, (1-EtInd)₂ZrMe₂, had the greatestdependence of Mw on H₂/C₂ ratio. The slopes may be used to selectcatalysts having widely divergent responses to hydrogen.

The data presented in FIGS. 2 and 3 and Tables 2 and 3 indicate that acombination of (1-EtInd)₂ZrCl₂ (B) and (PrCp)₂HfF₂ (I) will give apolymer with a broad MWD and SCBD without LCB. As shown in the plot 300in FIG. 3, the resins made with these two catalysts have MIR near 20and, thus, are essentially free of LCB. The information in Tables 2 and2 indicate that (1-EtInd)₂ZrCl₂ has approximately one third the Mw of(PrCp)₂HfF₂ at around 4.2 ppm/mol H₂/C₂. The information in the plot 200shown in FIG. 2, indicates that (1-EtInd)₂ZrCl₂ has approximately onefourth the SCB of (PrCp)₂HfF₂ under comparable conditions.

TABLE 3 Slope and intercept for plots of H₂/C₂ vs. 1/Mw for selectedMCNs Catalyst slope intercept 1 (CpMe₅)1-MeIndZrCl₂ 2.576E−06 4.932E−062 (1-EtInd)₂ZrCl₂ 3.533E−06 6.245E−06 3 (Me₄Cp) (1,3-Me₂Ind)ZrCl₂1.945E−06 5.436E−06 4 (PrCp)₂HfF₂ 1.342E−06 1.929E−06

The equations from Table 3 can be used to predict the amounts of(1-EtInd)₂ZrCl₂ needed in a combination with the catalyst (PrCp)₂HfF₂ tomake an overall resin with Mw of 100 Kg/mol at four different H₂ levels.These values may be used to set initial control points, for example, if(PrCp)₂HfF₂ is used as a supported catalyst component, and(1-EtInd)₂ZrCl₂ is a solution catalyst component, to be added as a trimcatalyst. In this embodiment, the amount of the (1-EtInd)₂ZrCl₂ catalystthat is added may be controlled to achieve Mw and other performancetargets. Results for various combinations are shown in Table 4.

TABLE 4 Mw of (1-EtInd)₂ZrCl₂ (lmw) and (PrCp)₂HfF₂ (hmw) as a functionof H₂/C₂ and fraction of low Mw polymer (F lmw) necessary to make anoverall Mw 100 Kg/mol H₂/C₂ lmw hmw/lmw hmw F lmw 4 49072 2.8 1370200.42 4.5 45157 2.8 125480 0.32 5 41821 2.8 115733 0.21 5.5 38944 2.8107391 0.11

Pilot Plant Runs using Trim Feed

The use of a catalyst trim feed to control the molecular weight andmolecular weight distribution was tested in a pilot plant, with theresults detailed in Table 5. In Table 5, the catalyst type correspondsto the numbered catalyst structures shown in the detailed description.Five of the catalyst runs (A-E) were control runs performed without theuse of a trim catalyst.

TABLE 5 Results from 13.25 Inch pilot plant reactor using trim addition.Trim H2/C2 Conc Run Catalyst Catalyst Form - Catalyst Al/Hf CatalystCatalyst Ratio No Type Dry/Slurry Support Mole Ratio Type (ppm/m %) AIII Dry 98.6 None 6.03 B III Dry 98.6 None 5.81 C III Slurry Spray Dried234 None 4.65 1 III Slurry Spray Dried 234 None 3.87 2 III Slurry SprayDried 234 IV-A, IV-B 3.79 3 III Slurry Spray Dried 234 IV-A, IV-B 3.78 4III Slurry Spray Dried 234 IV-C 3.81 5 III Slurry Spray Dried 234 IV-C3.80 6 III Slurry Spray Dried 234 IV-D 3.83 7 III Slurry Spray Dried 234IV-D 3.79 8 III Slurry Spray Dried 234 V-A 3.80 9 III Slurry Spray Dried234 V-A 3.79 D III Slurry Spray Dried 234 None 24.98 E III Slurry SprayDried 234 None 20.04 10 III Slurry Spray Dried 234 V-B 20.01 11 IIISlurry Spray Dried 234 V-B 20.12 12 III Slurry Spray Dried 234 IV-A,IV-B 3.60 13 III Slurry Spray Dried 234 IV-A, IV-B 3.81 C6/C2 Conc HighLoad Run Ratio Melt Index Melt Index MIR Density Cat No (m/m) (dg/min)(dg/min) (HLMI/MI) (g/cc) Prod. A 0.016352 1.21 41.8 34 0.9180 13,239 B0.014848 1.45 32.8 23 0.9168 13,071 C 0.01527 0.73 18.2 25.0 0.92017,801 1 0.01539 0.49 11.7 23.9 0.9194 7,373 2 0.01835 1.68 83.2 49.40.9340 9,956 3 0.01729 1.01 37.0 36.6 0.9281 8,300 4 0.01742 1.23 35.929.1 0.9274 8,233 5 0.01823 1.72 57.0 33.1 0.9315 8,767 6 0.01614 0.91421.3 23.3 0.9221 8,267 7 0.01709 1.090 27.8 25.5 0.9238 7,680 8 0.015950.602 14.6 24.3 0.9201 8,178 9 0.01724 0.702 19.0 27.1 0.9234 7,233 D0.00364 640 6866 10.7 0.9546 6,222 E 0.00388 399 6443 16.1 0.9543 7,72610 0.00409 86.3 2924 33.9 0.9501 3,988 11 0.01386 28.2 1325 47.0 0.94063,903 12 0.01692 0.401 13.4 33.5 0.9232 11,076 13 0.01953 0.287 10.837.8 0.9206 11,200

Controlling molecular weight distribution and composition distributionusing co-supported catalysts in combination with (CpPr)₂HfF₂.

Tests were run using a primary catalyst that included (CpPr)₂HfMe₂ (HfP,structure III). HfP is capable of polymerizing ethylene and mixtures ofethylene and comonomers in the presence of an activator and a support, acocatalyst, or both. The activator and support may be the same ordifferent. Multiple activators, supports and or cocatalysts may be usedsimultaneously. Cocatalysts may be added to modify any of theingredients. The descriptor catalyst, HfP, activator, supports and orcocatalysts refers to the actual compounds and also solutions of thesecompounds in hydrocarbon solvents.

For use as cocatalysts, especially in trim systems, the catalysts shouldbe soluble in alkane solvents such as hexane, paraffinic solvents, andmineral oil. The solubility may be greater than 0.0001 wt. %, greaterthan 0.01 wt. %, greater than 1 wt. %, or greater than 2%. Toluene mayalso be used as a solvent as the catalyst may be more soluble in anaromatic solvent

As described herein, a combination of HfP, an activator (MAO), and asupport (silica) was reacted with trim catalysts in hydrocarbon solventsto yield a polymerization catalyst with a different polymerizationbehavior than expected from the combination of the individualcomponents. More specifically, the molecular weight distribution for apolymer generated by the co-supported co-catalysts is broader than canbe achieved by mixtures of polymers formed from the individual componentcatalysts. This change in polymerization behavior is exemplified bychanges in the MWD, the CD, or MWD and CD of polymers formed by themixture of HfP and the selected cocatalysts. Thus, combining catalysts,HfP, activator and optionally a support, additional cocatalysts, orboth, in hydrocarbon solvents in an in-line mixer immediately prior to apolymerization reactor yields a new polymerization catalyst.

Any sequence of the combination of catalysts, HfP, activator andoptionally a support, additional cocatalysts, or both, in hydrocarbonsolvents may be used. For example, the catalysts may be added to amixture that includes HfP, activator and optionally a support,additional cocatalysts, or both. Further, catalysts and cocatalysts maybe added to a mixture of {HfP, activator and optionally a support}. Inaddition, catalysts and HfP may be added to a mixture that includes{activator and optionally a support and cocatalysts}.

It is desirable to combine the catalysts, HfP, the activator andoptionally a support, additional cocatalysts or both, in hydrocarbonsolvents then obtain a dry catalyst from the mixture. This dry mixturemay be fed directly, or as a slurry, into a polymerization reactor.

The change in the MWD and CD upon using the catalysts and HfP can becontrolled by changing the ratio of the catalysts to HfP. When nocatalysts are employed, the MWD and CD is that of HfP. When singlecatalysts are employed, the MWD and CD is that generated by thecatalysts themselves. Changing the ratio of catalysts changes the MWDand CD from that of the parents. The ratio can be changed to targetspecific MWD and CD targets.

Catalysts can be chosen to control the change in MWD or CD of thepolymer formed. Employing catalysts that yield lower or higher molecularweight polymers than HfP will broaden the molecular weight distribution.The response of the Mw of polymers made from the single componentsversus H2/C2 can be used as a guide for the selection. For example, acatalyst having less response to hydrogen than HfP will yield a higherMw than a polymer produced by HfP by itself, as shown in FIG. 2.Further, a catalyst having a higher response to hydrogen than HfP will,in a combination with HfP, yield a lower Mw than HfP by itself.

In addition to selecting catalysts to broaden the MWD, catalysts may beselected to change the composition distribution. For example, employingcatalysts that incorporate less or more comonomer than HfP will broadenthe composition distribution. A rough guide to this effect, as discussedfurther below, is the relative gas C6/C2 ratios required to prepare anapproximately 0.92 D resin from different catalysts. Those catalyststhat give larger differences in C6/C2 gas ratios from HfP will broadenthe CD more. Molecular weight distributions can also be changed byemploying a catalyst that yields a different MWD but similar averagemolecular weight to that from HfP.

The combination of catalysts with HfP can yield a MWD that is largerthan expected from the theoretical combination of the individualcatalysts. Desirable materials based on an HfP base catalyst are madewhen the Mw and comonomer incorporation abilities of the catalysts areboth higher than HfP. Similarly, desirable materials are also formedwhen the Mw and comonomer incorporation abilities of the catalysts areboth lower than HfP. Further, desirable materials are made when the Mwand of the catalysts are similar to and the comonomer incorporationabilities lower than HfP.

Making a Co-Supported Polymerization Catalyst

FIG. 4 is a flow chart of a method 400 for making a co-supportedpolymerization catalyst. The method 400 begins at block 402 with thegeneration of a plot of hydrogen/ethylene ratio versus the reciprocal ofmolecular weight of a polymer generated by each one of a number ofcatalysts. As discussed herein, the slope of each plot indicates theresponse of the corresponding catalyst to a hydrogen level.

At block 404, a value is determined for the comonomer/ethylene ratio foreach of the catalysts that can be used to achieve a single targetdensity, such as 0.92. The value of the ratio used to achieve the targetdensity indicates the ability of the catalyst to incorporate comonomer.At block 406, a first catalyst is selected for the co-supportedpolymerization catalyst. For example, the first catalyst can be acommonly used commercial catalyst, or may be selected to have a low or ahigh ability to incorporate comonomer and a high or low response tohydrogen.

At block 408, a second catalyst is selected for the co-supportedpolymerization catalyst. The second catalyst can be selected to have aslope of the plot for the hydrogen/ethylene ratio versus the reciprocalof molecular weight that is at least about 1.5 times as large as theslope of the plot for the first catalyst. Further, the second catalystcan be selected to have a value for the comonomer/ethylene ratio that isless than about 0.5 as large as comonomer/ethylene ratio of the firstcatalyst. At block 410, the first catalyst and the second catalyst canbe co-supported on a single support to create the co-supportedpolymerization catalyst, for example, using the trim techniquesdescribed herein, among others.

General Procedures for Forming Catalyst Components

Catalysts

Experimental

All manipulations were performed in an N₂ purged glovebox or usingstandard Schlenk techniques. All anhydrous solvents were purchased fromSigma-Aldrich and were degassed and dried over calcined Al₂O₃ beads ormolecular sieves prior to use. Toluene for the catalyst preparations waspre-dried with Al₂O₃ beads then dried over SMAO 757 before use.Deuterated solvents were purchased from Cambridge Isotope Laboratoriesand were degassed and dried over alumina beads or molecular sieves priorto use. Reagents used were purchased from Sigma-Aldrich, with theexception of ZrCl₄ 99+% which was purchased from Strem Chemicals, andbis(n-propyl-cyclopentadienyl)hafnium dimethyl (HfPMe₂) was purchasedfrom Boulder Scientific Lot# BSC3220-8-0002. ¹H NMR measurements wererecorded on a 250 Mz Bruker and a 500 Mz Bruker spectrometers.

Synthesis of Rac-meso-bis(1-Ethyl-indenyl)zirconium dimethyl(1-EtInd)₂ZrMe₂ (IV-A/IV-B)

Indenyllithium.

Freshly distilled indene (50.43 g, 434.1 mmol) was dissolved in 1 L ofpentane. Et₂O (25 mL) then 1.6M n-butyllithium in hexanes (268.5 mL,429.6 mmol) were added to the clear stirring solution over a span of 5min. A white solid precipitated and the supernatant took on a lightyellow color. After stirring overnight the suspension was filtered thendried in vacuo to yield a white solid (46.51 g, 381.0 mmol, 88.7%). ¹HNMR (THF-d₈): δ 5.91 (d, 2H), 6.44 (m, 2H), 6.51 (t, 1H), 7.31 (m, 2H).

1-Ethylindene.

46.51 g (380.95 mmol) of indenyllithium was dissolved in 250 mL of Et₂O,and a separate solution was made of 95.94 g (615.12 mmol) of ethyliodidein 400 mL of Et₂O. The ethyliodide solution was cooled to −30° C. in andthe indenyllithium solution was cooled to 0-10° C. using a dryice/acetone bath. The indenyllithium was added to the clear stirringsolution of ethylidode via cannula transfer. The solution became a lightyellow to yellow color upon addition of the indenyllithium solution. Thereaction was allowed to stir overnight and slowly warm to roomtemperature. After stirring overnight the flask was brought into the boxand the Et₂O was reduced in vacuo. Once LiI began to precipitate, 300 mLof pentane was added and the white suspension was filtered resulting ina light orange solution. The pentane was evaporated where more LiIprecipitated and a light orange oily liquid was obtained. The crudeproduct was distilled under diminished pressure using a rotary vacuumpump to a slight yellow clear liquid. ¹H NMR showed ˜90% 1-Ethylindeneand −10% 3-Ethylindene. Possible isomerization could have occurred dueto a small amount of acid present during the distillation as none waspresent in the crude ¹H NMR spectrum. 44.27 g (306.96 mmol) of productwas isolated for an 80.6% yield. ¹H NMR (CD₂Cl₂): δ 0.96 (3H, t), 1.59(1H, q), 1.99 (1H, q), 3.41 (1H, m), 6.58 (1H, d), 6.59 (1H, d), 7.24(2H, m), 7.41 (2H, dd).

1-Ethyl Indenyllithium.

44.27 g (306.98 mmol) of 1-Ethylindene containing ˜10% 3-Ethylindene wasdissolved in 500 mL of pentane and ca. 3 mL of Et₂O. To the clearstirring solution was added 188.28 mL (301.25 mmol) of 1.6Mn-butyllithium in hexanes over 10 minutes. Immediately a flaky whiteprecipitate formed and caused the stirring stop. The mixture wasmanually stirred to ensure proper incorporation of reagents and thesuspension was allowed to sit overnight. The suspension was filtered andthe white solid dried in vacuo. 43.27 g (288.18 mmol) of product wasobtained for a 95.7% yield. 1H NMR (THF-d8): δ 1.26 (3H, triplet), 2.86(2H, quartet), 5.72 (doublet, 1H), 6.38 (dd 1H), 6.43 (2H, m), 7.26 (1H,t), 7.30 (1H, m).

Rac-meso-bis(1-Ethyl-indenyl)zirconium dimethyl (1-EtInd)₂ZrMe₂ (IV-A/B)

7.00 g (46.65 mmol) of 1-Ethyl-indenyllithium was dissolved in 74 mL of1, 2-dimethoxyethane (DME) and a separate solution was made with 5.43 g(23.30 mmol) of ZrCl₄ in 75 mL of DME. To the clear ZrCl₄ solution wasadded the bright yellow solution of 1-ethyl-indenyllithium via pipetteover a fifteen minute period. Upon initial addition the solution took ona yellow color, and after 5 minutes into the addition a precipitateformed and an orange-yellow color ensued. Ten minutes into the additionthe supernatant turned orange with a yellow precipitate, and once allthe 1-ethyl-indenylltihium solution was added the mixture turned back toyellow. The reaction was allowed to stir overnight. A crude ¹H NMRspectrum of the slurry showed a rac/meso ratio of −1.1:1; however thiscan be misleading since the rac isomer is more soluble in DME than themeso isomer. Regardless of the isomer ratio, 15.61 mL (46.83 mmol) of3.0M CH₃MgBr in Et₂O was added in 1 mL portions over ten minutes. Afterthe tenth addition the yellow mixture turned an orangish color. Upon thefinal addition of the Grignard reagent, the mixture had turned brown andthe reaction was allowed to stir overnight. A ¹H NMR spectrum of thecrude mixture revealed a 1.1:1 meso/rac ratio. The DME was evaporatedand the brown solid was extracted with 3×20 mL of toluene plus anadditional 10 mL. The light brown solid obtained after solvent removalwas washed with 10 mL of pentane and dried in vacuo. 8.26 g (20.26 mmol)of the off-white solid was obtained for an 87% yield.

Dichloride spectral data: ¹H NMR (CD₂Cl₂): δ 1.16 (6.34H, t, rac), 1.24(6H, t, meso), 2.73-2.97 (8H, overlapping q), 5.69 (1.82H, dd, meso),5.94 (1.92H, dd, rac), 6.06 (1.99H, d, rac), 6.35 (1.84H, d, meso),7.22-7.65 (16H, m).

Dimethyl Spectral Data: ¹H NMR (C₆D₆): δ −1.40 (3.33H, s, meso), −0.895(6H, s, rac), −0.323 (3.34H, s, meso), 1.07 (13H, overlapping t), 2.47(4H, overlapping q), 2.72 (4H, q), 5.45-5.52 (8H, m), 6.91 (8H, m),7.06-7.13 (4H, m), 7.30 (4H, m).

Synthesis of Rac-meso-bis(1-Ethyl-indenyl)zirconium dimethyl(1-EtInd)₂ZrMe₂ (IV-A/B)

To a solution of ZrCl₄ (20.8 g; 89.3 mmol) in 1, 2-dimethoxyethane (DME)(ca. 100 mL) was added a solution of 1-ethyl-indenyllithium (26.8 g; 178mmol) dissolved in 1, 2-dimethoxyethane (DME) (ca. 200 mL) in portionsof about 5 mL over 15 minutes. Additional DME was added as necessary tokeep the reaction from becoming too thick to stir. The total volume atthe end of the addition was about 425 mL. Immediately prior to theaddition of the 1-Ethyl-indenyllithium solution and about halfwaythrough the addition, pentane (ca. 10 mL) was added to the reactionmixture and removed under vacuum in order to lower the temperature.After stirring about 4 h at room temperature an aliquot of the slurrywas removed and dried down. The 1H NMR of the solid thus obtained wastaken in CD₂Cl₂ and showed a rac/meso ratio of 0.7:1.

Approximately 100 mL of the solvent was evaporated from the reaction andmethyllithium solution (1.6 M in ether; 111 mL; 178 mmol) was added inportions (ca. 20 mL) over about an hour. After stirring overnight therac/meso ratio was 0.7:1.0. Additional MeLi solution (1.6 M in ether;7.0 mL; 11.2 mmol) was added and the reaction stirred at roomtemperature for 3 days. The rac/meso ratio was 0.9:1 as determined by ¹HNMR. The solvent was removed under vacuum and the residue was extractedwith warm hexanes (ca. 300 mL; 60° C.), filtered and concentrated toabout 100 mL total volume then cooled to −20° C. overnight. The solidwas isolated by filtration, washed with cold pentane (2×50 mL) and driedunder vacuum to give 29.2 g solid with a rac/meso ration of 0.94:1. Theisolated solid was extracted with warm hexane (ca. 150 mL) filtered awayfrom a small amount of pink solid. The volume was reduced to about 125mL and the solution was treated with trimethylsilylchloride (2.0 mL).The solution was filtered, concentrated to about 100 mL, heated tore-dissolve the precipitated product and allowed to cool slowly. Aftersitting overnight, the flask was cooled to −20 C which caused some pinksolid to precipitate. The flask was warmed to 55° C. and additionalhexanes (ca. 75 mL) was added along with trimethylsilylchloride (5.0mL). This was kept at 55° C. for two hours, the reaction was filtered togive a yellow solution. The solution was filtered, concentrated to about100 mL, heated to re-dissolve the precipitated product and allowed tocool slowly. The precipitated solid was isolated by filtration, washedwith cold pentane (2×30 mL), dried under vacuum at 55° C. The yield was21.1 g with a rac/meso ration of 1.19/1.

Synthesis of meso-(1-EtInd)₂ZrCl₂

1-Ethylindenyllithium (1.0 g; 6.7 mmol) was dissolved in dimethoxyethane(DME) (7.7 mL) and cooled to −20° C. Solid ZrCl₄ (0.781 g; 3.35 mmol)was added in portions over 5 minutes and the reaction was continuedovernight. After the volatiles were removed, the yellow solids thusobtained were extracted with CH₂Cl₂ until no yellow color remained. TheCH₂Cl₂ was removed under vacuum leaving a yellow solid. Yield=1.14 gwith a meso/rac ratio of 19:1.

Conversion of meso-(1-EtInd)₂ZrCl₂ to meso-(1-EtInd)₂ZrMe₂

meso-(1-EtInd)₂ZrCl₂ (1:19 rac/meso; 307 mg; 0.68 mmol) was slurried inEt₂O (ca. 10 mL) and MeMgBr (3.0 M in Et₂O; 0.47 mL; 1.41 mmol) wasadded. The reaction was dried down and extracted with warm hexanes (ca.18 mL at 60° C.), filtered and dried down to a light yellow solid (240mg). The ¹H NMR in C₆D₆ showed the rac/meso ratio of 1:19 was retained.

Conversion of 1:1 rac/meso-(1-EtInd)₂ZrCl₂ to 1:1rac/meso-(1-EtInd)₂ZrMe₂

(1-EtInd)₂ZrCl₂ (1:1 rac/meso; 12.2 g; 27.2 mmol) was slurried in Et₂O(ca. 80 mL) and MeMgBr (2.6 M in Et₂O; 23.2 mL; 60.3 mmol) was added.The reaction was stirred overnight, the reaction was dried down andextracted with warm hexanes (ca. 300 mL), filtered and about 1 mL of thesolution was dried down and the ¹H NMR in C₆D₆ showed a very clean 1:1meso/rac ratio of (1-EtInd)₂ZrMe₂.

Conversion of meso rich (1-EtInd)₂ZrCl₂ to close to 1:1 rac/meso(1-EtInd)₂ZrMe₂

meso-(1-EtInd)₂ZrCl₂ (1:5 rac/meso; 244 mg; 0.54 mmol) was slurried inEt₂O (ca. 5 mL) and MeLi (1.6 M in Et₂O; 0.69 mL; 1.10 mmol) was added.The reaction was stirred overnight, filtered and an aliquot of thefiltered reaction mixture was dried down. The ¹H NMR in C₆D₆ showed a1:1.24 rac/meso ratio.

Synthesis of (1-Methylindenyl)(pentamethylcyclopentadienyl)zirconium(IV)dimethyl (IV-C)

(1-Methylindenyl)(pentamethylcyclopentadienyl)zirconium(IV)dichloride

In the drybox, weighed 1-Methyl-1H-indene oil (1.85 g, 14.2 mmol) into a250 ml roundbottom flask and dissolved in 25 ml dry diethyl ether. Addedn-Butyllithium (1.6 M in hexanes, 12.0 ml, 19.2 mmol) dropwise from a 20ml needle/syringe to form a yellow solution. Stirred at room temperaturefor 60 minutes.

To the yellow-orange solution of (1-Methyl)indenyllithium was addedCp*ZrCl₃ (4.51 g, 13.5 mmol, used as received from Aldrich-475181)quickly in one portion as a yellow crystalline solid. Stirred theyellow-orange slurry overnight at room temperature.

Mixture allowed to settle for 30 min. Dark brown solution was decantedfrom pale yellow solids, rinsed solids on glass frit with 100 ml dryether. Extracted solids on frit with 100 ml dichloromethane, affording ayellow suspension. Filtered through Celite plug on frit and evaporatedvolatiles to yield a yellow solid. Recrystallized from ether/pentane toafford 2.70 g (47%). Additional material obtained from mother liquor:1.19 g (20%)

¹H NMR (C₆D₆, 500 MHz, 35° C.): δ 1.70 (15H, s, Cp*), 2.30 (3H, s,indenyl CH₃), 5.56 (2H, ABq, indenyl CH, CH), 7.05 (1H, dd, indenyl CH),7.10 (1H, dd, indenyl CH), 7.24 (1H, dt, indenyl CH), 7.56 (1H, dq,indenyl CH).

(1-Methylindenyl)(pentamethylcyclopentadienyl)zirconium(IV)dimethyl(IV-C)

(1-Methylindenyl)(pentamethylcyclopentadienyl)zirconiumdichloride (4.92g, 11.5 mmol) was slurried in 50 mL diethyl ether and cooled to −50° C.To this, a solution of MeLi (14.8 mL of a 1.71M solution in diethylether, 25.4 mmol) was added slowly by syringe. The mixture was left tostir and slowly warm to room temperature to give a pink slurry. After 16h, the solvent was removed under vacuum and the residue extracted withtoluene. The insolubles were removed by filtering through a frit linedwith Celite and the solvent was removed to give an orange oily solid.The solid was washed with pentane and dried under vacuum (3.89 g, 88%yield). ¹H NMR δ (C₆D₆): 7.53 (d, 1H, 8-IndH), 7.13-6.99 (m, 3H,5,6,7-IndH), 5.21 (d, 1H, 2-IndH), 5.11 (d, 1H, 3-IndH), 2.20 (s, 3H,1-MeInd), 1.69 (s, 15H, CpMe₅), −0.51 (s, 3H, ZrMe), −1.45 (s, 3H,ZrMe).

Synthesis of (1,3-dimethylindenyl)(tetramethylcyclopentadienyl)Zirconiumdimethyl[(1,3-Me₂Ind)(CpMe₄)]ZrMe₂ (IV-D)2,3,4,5-tetramethyl-1-trimethylsilyl-cyclopenta-2,4-diene

To a 2 liter Erlenmeyer flask, dissolved yellow oil oftetramethylcyclopentadiene (50 g, 409 mmol—obtained from BoulderScientific) in 1 liter of anhydrous THF. Stirred at room temperature asn-butyllithium (175 ml, 437 mmol) added through a 60 ml plastic syringewith a 20 gauge needle regulating dropwise flow. Formation of a paleyellow precipitate was observed. Reaction is a yellow slurry uponcomplete addition of lithium reagent. Stirred 1 hr at room temperature,then with vigorous stirring chlorotrimethylsilane (60 ml, 470 mmol) wasadded and reaction allowed to stir overnight at room temperature. Afterstirring at room temperature for 15 hr, mixture is a yellow solution.Removed THF solvent with under a stream of N₂ to afford an oily residue,which was then extracted with 1 liter of dry pentane and filteredthrough a celite pad on coarse frit. Removed volatiles under vacuum toafford product as a yellow oil: 62.9 g, 79%. ¹H NMR (C₆D₆, 250 MHz): δ−0.04 (s, Si(CH₃)₃), δ 1.81, (s, CH₃), δ 1.90 (s, CH₃), δ 2.67 (s, CH)

Synthesis of (tetramethylcyclopentadienyl)zirconium trichloride

In a drybox, charged solid ZrCl₄ (30.0 g, 129 mmol) to a 450 mlChemglass pressure vessel with magnetic spinbar, suspended in 100 ml drytoluene. Dispensed2,3,4,5-tetramethyl-1-trimethylsilyl-cyclopenta-2,4-diene as a yellowoil (27.5 g, 142 mmol) and rinsed down with additional 100 ml drytoluene. Sealed pressure vessel with threaded cap with Viton o-ring, andheated on a fitted aluminum heating mantle to 110° C. for 90 min.Solution darkens with time, and insolubles were present during reaction.Vessel was allowed to stir overnight and cool to room temperature.Vessel was opened and solvent volume reduced under stream of N₂,affording a thick red sludge. Extracted with 2×50 ml dry pentane thenwith 100 ml dry ether. Red solution removed and recovered product aspale red solid: 35.4 g, 85%. ¹H NMR (C₆D₆, 250 MHz): δ 1.89 (br s, CH₃),δ 2.05 (br s, CH₃), δ 5.78 (br s, CH)

Synthesis of 1,3-dimethylindene

1-Methyl-indenyllithium: Freshly distilled 3-Methylindene (33.75 g259.24 mmol) was dissolved in pentane (1 L). Et₂O (10 ml), then 1.6Mn-butyllithium in hexanes (107 mL, 171.2 mmol) and 2.5M n-butyllithiumin hexanes (34.2 mL, 85.5 mmol) were added to the clear stirringsolution. Immediately a flaky white solid precipitated. After stirringovernight, the suspension was filtered and the white solid dried invacuo (33.88 g, 248.90 mmol, 97%). 1H NMR (THF-d8): δ 2.41 (s, 3H), 5.68(d, 1H), 6.31 (d, 1H), 6.41 (m, 2H), 7.22 (m, 2H).

In a drybox, iodomethane (2.0 ml, 32.1 mmol) was dissolved in 80 ml drydiethyl ether in a 250 ml round bottom flask with magnetic spinbar.Flask was placed in a isohexane cold bath (−25° C.) in a wide mouthdewar. In a separate 100 ml Erlenmeyer flask, a room temperaturesolution of 1-methylindenyl lithium (3.50 g, 25.7 mmol) was prepared in50 ml dry diethyl ether, affording a yellow solution. Slow, dropwiseaddition of indenyl lithium solution to the cold, stirred solution ofiodomethane was performed over 15 min. Continued stirring at lowtemperature for 30 min, then removed the cold bath and allowed thereaction to warm to room temperature overnight. Solution is turbid whiteafter stirring 15 hr at room temperature. Reduced solution volume undernitrogen flow, then volatiles evaporated under high vacuum. Extractedsolids with 2×80 ml isohexane and filtered through pad of celite oncoarse frit. Filtrates evaporated under high vacuum to afford brown oil.Dissolved in 5 ml dichloromethane and loaded via pipet onto silica gelcolumn (Biotage SNAP 100 g), eluting with dichloromethane:isohexane(gradient, 2-20%). Fractions combined and evaporated to afford a clearoil. Collected 2.54 g, 68%.

¹H NMR (C₆D₆, 500 MHz): δ 1.11 (d, J=7.5 Hz, —CHCH₃), δ 1.96 (s,CH═CCH₃), δ 3.22 (m, CHCH₃), δ 5.91 (m, CH═CCH₃), δ 7.15-7.27 (aromaticCH). Mixture contains minor isomer 3,3-dimethylindene in 1:10 ratio withdesired product. δ 1.17 (s, CH₃), δ 6.14 (d, J=5.5 Hz, CHH), δ 6.51 (d,J=5.5 Hz, CHH).

Synthesis of 1,3-dimethylindenyl lithium

Dissolved 2.54 g (17.6 mmol) of clear oil, 10:1 mixture of1,3-dimethylindene and 3,3-dimethylindene, in 35 ml dry pentane. Stirredat room temperature as 6.2 ml of a 2.5 M hexane solution ofn-butyllithium (15.5 mmol) was added slowly, dropwise. White precipitateformed immediately. Stirred at room temperature for 45 min, thenfiltered supernatant via cannula. Suspended the residue in 30 ml drypentane and cooled in drybox freezer (−27° C.) for 60 min. Filteredsupernatant and dried in vacuo to white powder, 2.34 g (88%) and usedas-is for subsequent reaction step without characterization.

Synthesis of[(1,3-dimethylindenyl)(tetramethylcyclopentadienyl)]Zirconium dichloride

Weighed 3.50 g (10.98 mmol) tan powder of(tetramethylcyclopentadienyl)zirconium trichloride into a 100 ml flatbottom glass bottle with magnetic spinbar. Suspended in 80 ml drydiethyl ether. Stirred as 1,3-dimethylindenyl lithium (1.65 g, 10.99mmol) added as powder over several minutes. Rinsed down with additional20 ml ether. Capped bottle and stirred overnight at room temperature.Mixture a yellow slurry after stirring 15 hr at room temperature.Evaporated volatiles under high vacuum, then extracted residue with 2×80ml dichloromethane. Filtered through celite pad on coarse frit.Concentrated in vacuo and filtered again through fresh celite on coarsefrit. Dried in vacuo to free flowing yellow powder, 3.6 g (77%). ¹H NMR(CD₂Cl₂, 500 MHz): δ 1.89 (s, CH₃ of Cp^(Me4)), δ 1.90 (s, CH₃ ofCp^(Me4)), δ 2.40 (s, CH₃ of C₉ fragment), δ 5.67 (s, CH of Cp^(Me4)), δ6.33 (s, CH of C₉ fragment), δ 7.24 (AA′BB′, aromatic CH of C₉fragment), δ 7.52 (AA′BB′, aromatic CH of C₉ fragment). Contains ca. 15%diethyl ether.

Synthesis of[(1,3-dimethylindenyl)(tetramethylcyclopentadienyl)]Zirconium dimethyl(IV-D)

In the drybox, suspended bright yellow powder of(1,3-Me₂Ind)(Cp^(Me4))ZrCl₂ (3.6 g, 8.4 mmol) in 75 ml dry diethyl etherin a 100 ml amber glass flat-bottom bottle with magnetic spinbar. Cooledbottle to −10 C in isohexane bath, stirred as solution of methyllithium(1.6 M in ether) delivered via syringe in portions (4×3 ml, 19.2 mmol).Capped bottle with septum and stirred overnight, allowing cold bath toslowly warm to room temperature. Evaporated slurry to dryness under highvacuum. Extracted with 3×50 ml dichloromethane and filtered throughcelite on coarse frit. Concentrated under stream of nitrogen, then addedpentane. Stirred 15 min then evaporated volatiles. Washed solids withcold pentane, dried in vacuo. Collected as tan powder, 1.67 g; secondcrop recovered from filtrate, 0.52 g. Combined yields 2.19 g, 67%. ¹HNMR (CD₂Cl₂, 500 MHz): δ −1.22 (s, ZrCH₃), 1.78 (s, CH₃ of Cp^(Me4)fragment), 1.87 (s, CH₃ of Cp^(Me4) fragment), 2.25 (s, CH₃ of C₉fragment), 4.92 (s, CH of Cp^(Me4) fragment), 5.60 (s, CH of C₉fragment), 7.14 (AA′BB′, aromatic CH of C₉ fragment), 7.44 (AA′BB′,aromatic CH of C₉ fragment). ¹³C{¹H} NMR (CD₂Cl₂, 125 MHz): δ 11.64 (CH₃of Cp^(Me4) fragment), 12.91 (CH₃ of of C₉ fragment), 13.25 (CH₃ ofCp^(Me4) fragment), 37.23 (ZrCH₃), 106.34 (CH of Cp^(Me4) fragment),115.55 (CH of C₉ fragment); quaternary ¹³C resonances 107.36, 117.51,122.69, 125.06.

Synthesis of Meso-O(1-SiMe2Indenyl)2Zirconium dimethyl (V-A)

To a slurry of meso-O—(SiMe₂Indenyl)₂ZrCl₂ (purchased from Süd-ChemieCatalytica; 40.0 g; 83.2 mmol) in about 300 mL of ether was added 54.0mL of MeMgBr (3.0 M/ether; 162 mmol) at room temperature. After stirringthe slurry for 1.5 hours, the volatiles were removed; heptane (about 300mL) was added to the resultant solid and heated to 80° C. for 30minutes. The slurry was filtered and the supernatant was cooled to −30°C. resulting in the formation of a crystalline solid that was isolatedby filtration, washed with pentane and dried under vacuum. The yield was26.0 g. ¹HNMR δ (C₆D₆): 7.57 (m, 2H), 7.42 (m, 2H), 7.02 (m, 2H), 6.94(m, 2H), 6.31 (d, 2H), 5.82 (d, 2H), 0.44 (s, 6H), 0.34 (s, 6H), 0.00(s, 3H), −2.07 (s, 3H).

Catalyst Preparations

Dehydration of Silica at 610° C.

Ineos ES757 silica (3969 g) was charged into a dehydrator (6 ft length,6.25 in diameter) equipped with a 3-zone heater then fluidized with dryN2 gas at a flow rate of 0.12 ft³/s. Afterwards, the temperature wasraised to 200° C. in a 2 h period. After holding at 200° C. for 2 h, thetemperature was raised to 610° C. in a 6 h period. After holding at 610°C. for 4 h, the temperature was allowed to cool to ambient temperatureover a 12 h period. The silica was transferred under N₂ to an APC canthen stored under N₂ pressure (20 psig).

Preparation of Methyl Aluminoxane Supported on Silica (SMAO)

In a typical procedure, Ineos ES757 silica (741 g), dehydrated at 610°C., was added to a stirred (overhead mechanical conical stirrer) mixtureof toluene (2 L) and 30 wt % solution of methyl aluminoxane in toluene(874 g, 4.52 mol). The silica was chased with toluene (200 mL) then themixture was heated to 90° C. for 3 h. Afterwards, volatiles were removedby application of vacuum and mild heat (40° C.) overnight then the solidwas allowed to cool to room temperature.

Typical Small Scale Catalyst Preparation for Laboratory Salt Bed Reactor

In a N2 purged drybox, 3.00 grams of SMAO (4.5 mmol MAO/g SMAO) weretransferred to a 125 ml Cel-Stir mixer. Pentane (50 mL) was added tocreate a slurry. The slurry was stirred at ambient temperature. Themetallocene (0.11 mmol) was dissolved in a minimal amount of toluene (˜2mL). This solution was then added to the stirring slurry. The mixturewas allowed to stir for one hour. After the allotted time, the mixturewas filtered onto a glass frit and washed with fresh pentane (2×10 mL)then dried for at least one hour.

Description of Laboratory Salt Bed Reactor

Under a N₂ atmosphere, a 2 L autoclave was charged with dry salt (200 g)and SMAO (3 g). At a pressure of 2 psig N₂, dry, degassed 1-hexene (seeTable 6) was added to the reactor with a syringe. The reactor wassealed, heated to 80° C. while stirring the bed, then charged with N₂ toa pressure of 20 psig. Then, solid catalyst was injected into thereactor with ethylene at a pressure of 220 psig; ethylene flow wasallowed over the course of the run. The temperature was raised to 85° C.Hexene was fed into the reactor as a ratio to ethylene flow (0.08 g/g).Hydrogen was fed into the reactor as a ratio to ethylene flow per thedescription in the table. The hydrogen and ethylene ratios were measuredby on-line GC analysis. Polymerizations were halted after 1 h by ventingthe reactor, cooling to room temperature then exposing to air. The saltwas removed by stirring the crude product in water. The polymer wasobtained by filtration then drying in a vacuum oven.

TABLE 6 Feed conditions for laboratory salt-bed reactor experiments FeedFeed Initial Ratio Ratio Amount of SMAO- Charge Initial Charge C6/C2H2/C2 cat used Metallocene C6 (mL) H2 (sccm) (g/g) (mg/g) (mg) IV-A/B 20 0.08 0 18.3 IV-A/B 2 17 0.08 0 41.5 IV-A/B 2 100 0.08 3 43.5 IV-C 2 00.08 0 18.3 IV-C 3 10.5 0.08 0 40.3 IV-C 4.9 10.5 0.08 0 38.9 IV-C 3 450.08 3 43.5 IV-C 3 400 0.08 3 43.5 IV-D 2 51 0.08 0 30.4 IV-D 2 51 0.080 30.7 III 2 261 0.08 1 50.8 III 2 300 0.08 1 30.4 III 2 0 0.08 0 41.7III 2 100 0.08 3 40.1

TABLE 7 Polymerization results for laboratory salt-bed reactorexperiments SCB Average Content SMAO- Productivity H2/C2 Mn/ Mw/ Mz/Me/1000C Metallocene (g/g) (ppm/mol) 1000 1000 1000 Mw/Mn (Corr) IV-A/B1530 0.5 39 131 278 3.4 6.1 IV-A/B 1525 0.5 40 126 264 3.2 6.0 IV-A/B993 4.2 11 47 116 4.3 5.3 IV-C 1350 0.2 57 204 471 3.5 3.4 IV-C 1953 0.257 187 371 3.3 4.9 IV-C 1900 0.5 34 145 312 4.2 6.2 IV-C 777 4.3 13 60134 4.6 3.8 IV-C 805 6.3 9 48 118 5.6 3.4 IV-D 1751 0.3 39 168 427 4.36.1 IV-D 641 4.3 19 73 142 3.8 3.8 III 3510 2.0 69 193 432 2.8 12.5 III4846 4.2 43 114 220 2.7 9.5 III 4825 4.8 47 133 269 2.8 12.1 III 467710.2 21 63 128 3.0 10.3

Large Scale Catalyst Preparations for 24-Inch Diameter Gas-Phase PilotPlant Testing

A 5 L 3-neck Morton flask was charged with pentane (4 L) then stirred(140 rpm) with a mechanical stirrer while charged with SMAO (375 g). Asolution containing (1-EtInd)₂ZrMe₂ (IV-A/B), HfPMe₂ (III), and toluenewas added with an addition funnel over the course of an hour. The slurrytook on a green color and was allowed to stir for an additional hour.The mixture was then filtered and dried in vacuo for a total of 8 hours.Results are shown in Table 8.

TABLE 8 Blend Combinations (1EtInd)2ZrMe2 (CpPr)2HfMe2 (IV-A/B) (III)(1EtInd)2ZrMe2 mass (g) mmol mass (g) mmol mole fraction 2.89 7.09 8.8620.95 0.25 2.87 7.04 8.94 21.14 0.25 5.75 14.10 5.97 14.12 0.50 5.7514.10 5.97 14.12 0.50

75% HfPMe₂/25% (1-EtInd)₂ZrMe₂ Catalyst Preparation Batch 2

A similar procedure as described above was employed for the second batchof 75/25 catalyst. A mixture of SMAO was used comprising of 204.15 gfrom UT-331-142, 176.17 g from UT-331-101, 209.49 g from UT-331-124, and160.19 g form UT-331-143. For the second batch, 4 L of pentane was addedfirst to the Morton flask followed by the SMAO so clumping would notoccur. Two separate solutions were made with 2.87 g (7.09 mmol) of(1-EtInd)₂ZrMe₂ and 8.94 g (20.95 mmol) of HfPMe2 in 20 mL of toluene.

50% HfPMe₂/50% (1-EtInd)₂ZrMe₂ Catalyst Preparation Batch 1 & 2

The same procedure used to prepare the second batch of 75/25 catalystwas used for both sets of 50/50 catalyst. Batch 1 used SMAO fromUT-331-143, 5.75 g (14.10 mmol) of (1-EfInd)₂ZrMe₂, and 5.97 g (14.11mmol) of HfPMe₂. Batch 2 used SMAO from UT-331-144, 5.75 g (14.09 mmol)of (1-EtInd)₂ZrMe₂, and 5.97 g (14.11 mmol) of HfPMe₂.

Mixing of the Catalysts

The two 75/25 batches were combined in a 4 L Nalgene bottle and manuallymixed by spinning and shaking the bottle. The two 50/50 batches werealso mixed in the same manner.

Spray-Dried Catalyst Preparations

Spray Dried HfP Low (SD-(III)). The feed stock slurry was prepared byfirst adding 10 wt % MAO (24.7 lbs), toluene (35.8 lbs) and CabosilTS-610 (3.4 lbs) to a 10 gallon feed tank. The mixture was stirredovernight at room temperature. HfP (III) (28.75 g, 0.06798 mol) wasadded then the resulting slurry was mixed for another hour at −38-40° C.before spraying. The catalyst was spray dried at a slurry feed rate of93 lb/h, 90% atomizer speed, and outlet temperature of 80° C. Yield was2289 g (85%). Analytical data are reported in Table 9.

TABLE 9 Analytical data for supported HfP (III) Al mmol/g Hf microCatalyst wt % Al wt % Hf actual mol/g Al/Hf actual SD-(III) 16.0 0.735.9 41 145

Description of 24-Inch Diameter Gas-Phase ReactorReactor

The polymerization was conducted in a continuous gas phase fluidized bedreactor having a straight section of 24 inch (61 cm) diameter with alength of approximately 11.75 feet (3.6 m) and an expanded section of10.2 feet (3.1 m) length and 4.2 feet (1.3 m) diameter at the largestwidth. The fluidized bed is made up of polymer granules, The gaseousfeed streams of ethylene and hydrogen together with liquid 1-hexene weremixed together in a mixing tee arrangement and introduced below thereactor bed into the recycle gas line. The individual flow rates ofethylene, hydrogen and 1-hexene were controlled to maintain fixedcomposition targets. The ethylene concentration was controlled tomaintain a constant ethylene partial pressure. They hydrogen wascontrolled to maintain a constant hydrogen to ethylene mole ratio. Theconcentrations of all gasses were measured by an on-line gaschromatograph to ensure relatively constant composition in the recyclegas stream.

The solid catalyst was injected directly into the fluidized bed usingpurified nitrogen as a carrier. Its rate of injection was adjusted tomaintain a constant production rate of the polymer. The reacting bed ofgrowing polymer particles was maintained in a fluidized state bycontinually flowing the makeup feed and recycle gas through the reactionzone at a superficial gas velocity 1-3 ft/sec (0.3 to 0.9 m/sec). Thereactor was operated at a total pressure of 300 psig (2068 kPa gauge).To maintain a constant reactor temperature, the temperature of therecycle gas was continuously adjusted up or down to accommodate anychanges in the rate of heat generation due to the polymerization.

A solution of anti-static agents in hexane (1:1 Aluminum stearate:N-nonyldiethanolamine at 20 wt %) was fed into the reactor using amixture of iso-pentane and nitrogen at such a rate as too maintain ca.30 ppm anti-static agents in the fluidized bed.

The fluidized bed was maintained at a constant height by withdrawing aportion of the bed at a rate equal to the rate of formation ofparticulate product. The product was removed semi-continuously via aseries of valves into a fixed volume chamber, which was simultaneouslyvented back to the reactor to allow highly efficient removal of theproduct, while at the same time recycling a large portion of theunreacted gases back to the reactor, This product was purged to removeentrained hydrocarbons and treated with a small stream of humidifiednitrogen to deactivate any trace quantities of residual catalyst andcocatalyst.

Run Summary

Examples of run conditions for the polymerizations are shown in Table10.

TABLE 10 Run conditions for polymerizations in 24-Inch DiameterGas-Phase Reactor Polymerization Example MCNs 3:1 3:1 3:1 (III)(III):(IV-A/B) (III):(IV-A/B) (III):(IV-A/B) Cat Density gm/cc 0.34 0.400.40 0.40 Total Polymer Produced 4853 11386 4452 3058 Bed Turnovers(whole part) 6.98 16.42 6.41 4.40 Residence Time 4.21 4.26 4.48 4.55 C2Concentration (mole %) 69.9 70.1 70.0 70.0 C2 Partial Pressure (psia)220 220 220 220 H2 Concentration (ppm) 293 315 296 232 H2/C2 AnalyzerRatio 4.19 4.50 4.23 3.31 (ppm/mole %) Hexene conc (mole %) 1.20 1.901.47 1.56 C6/C2 Analyzer Ratio 0.0172 0.0271 0.0210 0.0223 C2 Feed(lb/hr) 187 199 189 182 H2/C2 Flow Ratio (Mlb/lb) 0.059 0.166 0.1490.116 C6/C2 Flow Ratio 0.0988 0.1335 0.0991 0.1040 IC5 (mole %) 2.5 2.22.4 2.3 N2 Conc (mole %) 26.39 25.77 26.08 26.03 Reactor Vent Rate(lb/hr) 16.67 17.57 7.08 18.15 Reactor Pressure (psia) 314.5 314.5 314.2314.6 Bed Temperature (deg C.) 78.8 78.8 78.7 78.7 Exchanger dp (psi)0.409 0.380 0.400 0.416 Plate dp (″H2O) 91.97 92.24 90.62 91.48 GasVelocity (ft/sec) 2.25 2.25 2.25 2.25 Bed Weight (lbs) 695.4 693.4 694.1695.7 Bed Level (ft) 14.2 13.4 13.1 13.0 Fluidized Bed Density (lb/ft3)17.80 18.95 19.08 19.07 Exp sect diff press (inch H20) 6.35 4.96 4.594.63 Cat Feed Rate (seconds) 21.00 15.00 16.00 16.00 Cat feed rate(g/hr) 9.07 12.43 11.55 11.55 Cat Feeder Efficiency (%) 1.10 0.93 0.920.92 N2 Sweep with Continuity Additive 1.3 1.3 1.3 1.3 lb/hr IC5 Flushwith Continuity Additive 4.1 4.0 4.1 4.0 lb/hr N2 flow to annulus withcat lb/hr 3.0 3.2 3.2 3.2 N2 flow with Cat lb/hr 3.0 3.0 3.0 3.0Production Rate (lb/hr) Drops 165.0 162.8 155.0 152.8 Cat Activity matlbalance (gm/gm) 8264 5944 6092 6005 Drops Melt Index (I2) 0.93 1.06 1.230.72 HLMI (I21) 27.23 61.67 67.01 38.17 MFR (I21/I2) 29.28 58.18 54.4853.09 Density (gm/cc) 0.9196 0.9210 0.9263 0.9253 Polymerization ExampleCatalyst Example MCNs 1:1 1:1 1:1 (III):(IV-A/B) (III):(IV-A/B)(III):(IV-A/B) Cat Density gm/cc 0.38 0.38 0.38 Total Polymer Produced4338 3624 2359 Bed Turnovers (whole part) 6.26 5.22 3.43 Residence Time5.19 4.86 5.58 C2 Concentration (mole %) 69.8 70.0 69.0 C2 PartialPressure (psia) 220 220 200 H2 Concentration (ppm) 294 321 192 H2/C2Analyzer Ratio (ppm/mole %) 4.21 4.59 2.78 Hexene conc (mole %) 1.742.14 2.41 C6/C2 Analyzer Ratio 0.0249 0.0305 0.0350 C2 Feed (lb/hr) 172174 89 H2/C2 Flow Ratio (Mlb/lb) 0.185 0.197 0.106 C6/C2 Flow Ratio0.0988 0.1330 0.1347 IC5 (mole %) 2.4 2.2 2.3 N2 Conc (mole %) 26.0025.60 26.30 Reactor Vent Rate (lb/hr) 11.90 19.82 45.33 Reactor Pressure(psia) 314.4 314.6 289.9 Bed Temperature (deg C.) 78.9 78.8 78.2Exchanger dp (psi) 0.373 0.385 0.433 Plate dp (″H2O) 92.07 92.45 96.76Gas Velocity (ft/sec) 2.25 2.25 2.24 Bed Weight (lbs) 693.5 694.6 688.4Bed Level (ft) 13.3 13.7 12.6 Fluidized Bed Density (lb/ft3) 18.96 18.5119.88 Exp sect diff press (inch H20) 4.98 5.91 4.08 Cat Feed Rate(seconds) 17.00 17.00 16.00 Cat feed rate (g/hr) 10.63 10.63 11.30 CatFeeder Efficiency (%) 0.94 0.94 0.94 N2 Sweep with Continuity Additivelb/hr 1.3 1.3 1.3 IC5 Flush with Continuity Additive lb/hr 4.0 4.0 3.6N2 flow to annulus with cat lb/hr 3.2 3.2 3.2 N2 flow with Cat lb/hr 3.03.0 3.0 Production Rate (lb/hr) Drops 133.5 143.0 123.3 Cat Activitymatl balance (gm/gm) Drops 5700 6106 4955 Melt Index (I2) 4.86 6.17 2.20HLMI (I21) 239.08 319.27 99.04 MFR (I21/I2) 49.19 51.75 45.02 Density(gm/cc) 0.9319 0.9257 0.9254

Description of 13.25 Inch Diameter Gas-Phase Reactor

A gas phase fluidized bed reactor of 0.35 meters internal diameter and2.3 meters in bed height was utilized for polymerizations, with theresults shown in Table 11. The fluidized bed was made up of polymergranules and the gaseous feed streams of ethylene and hydrogen togetherwith liquid 1-hexene comonomer were introduced below the reactor bedinto the recycle gas line. The individual flow rates of ethylene,hydrogen and 1-hexene were controlled to maintain fixed compositiontargets. The ethylene concentration was controlled to maintain aconstant ethylene partial pressure. The hydrogen was controlled tomaintain constant hydrogen to ethylene mole ratio. The concentrations ofall the gases were measured by an on-line gas chromatograph to ensurerelatively constant composition in the recycle gas stream. The reactingbed of growing polymer particles was maintained in a fluidized state bythe continuous flow of the make-up feed and recycle gas through thereaction zone. A superficial gas velocity of 0.6-0.9 meters/sec was usedto achieve this. The fluidized bed was maintained at a constant heightby withdrawing a portion of the bed at a rate equal to the rate offormation of particulate product. The polymer production rate was in therange of 15-25 kg/hour. The product was removed semi-continuously via aseries of valves into a fixed volume chamber. This product was purged toremove entrained hydrocarbons and treated with a small stream ofhumidified nitrogen to deactivate any trace quantities of residualcatalyst.

The solid catalyst was dispersed in degassed and dried mineral oil as anominal 18 wt % slurry and contacted with the trim catalyst solution fora few seconds to minutes before being injected directly into thefluidized bed using purified nitrogen and isopentane as carriers in amanner that produces an effervescence of nitrogen in the liquid andspray to aid in dispersing the catalyst. The trim catalyst was providedinitially as a solution, and substantially diluted with isopentane to aconcentration of about 0.015 wt % before being mixed in-line with theslurry catalyst component in a continuous manner prior to injection tothe reactor. The relative feeds of the slurry catalyst and the trimcatalyst were controlled to achieve an aim target feed ratio of theiractive polymerization metals, and the feeds adjusted accordingly foroverall polymer production rate and the relative amounts of polymerproduced by each catalyst based somewhat on polymer flow index MFR anddensity, while also manipulating reaction temperature and the gascompositions in the reactor. The reacting bed of growing polymerparticles was maintained in a fluidized state by continually flowing themakeup feed and recycle gas through the reaction zone at a superficialgas velocity in about the range of 2.0 to 2.2 ft/sec (0.61 to 0.67m/sec). The reactor was operated at a total pressure of about 350 psig(2413 kPa gauge). To maintain a constant fluidized bed temperature inthe reactor, the temperature of the recycle gas was continuouslyadjusted up or down by passing the recirculating gas through the tubesof a shell-and-tube heat exchanger with cooling water on the shell-sideto accommodate any changes in the rate of heat generation due to thepolymerization.

A slurry mixture of anti-static agents in degassed and dried mineral oil(1:1 Aluminum stearate: N-nonyldiethanolamine at 20 wt % concentration)was fed into the reactor using a mixture of iso-pentane and nitrogen atsuch a rate as to achieve a concentration of between 38 and 123 ppmwanti-static agents in the fluidized bed. (row 128) Isopentane and/ornitrogen was optionally employed to assist in conveying and dispersingthe slurry mixture of anti-static into the reactor fluidized bed via a ⅛inch to 3/16 inch OD injection tube thief extending a few inches intothe bed from the reactor side wall.

The fluidized bed was maintained at a constant height by withdrawing aportion of the bed at a rate equal to the rate of formation ofparticulate product. The product was removed semi-continuously via aseries of valves into a fixed volume discharge chamber. This product waspurged to remove entrained hydrocarbons and treated with a small streamof humidified nitrogen immediately on discharge to a receiving fiberpakdrum to deactivate any trace quantities of residual catalyst andcocatalyst.

All numerical values are “about” or “approximately” the indicated value,and take into account experimental error and variations that would beexpected by a person having ordinary skill in the art. Further, variousterms have been defined above. To the extent a term used in a claim isnot defined above, it should be given the broadest definition persons inthe pertinent art have given that term as reflected in at least oneprinted publication or issued patent. All patents, test procedures, andother documents cited in this application are fully incorporated byreference to the extent such disclosure is not inconsistent with thisapplication and for all jurisdictions in which such incorporation ispermitted.

TABLE 11 Polymerization Experiments in 13.25 Inch Diameter Gas-PhaseReactor Polymerization Example 1 2 3A 3B Trim Metallocene None NoneIV-A/B IV-A/B Base Catalyst SD-(III) SD-(III) SD-(III) SD-(III) Part BedTurnovers Averaging Data 1.81 1.80 1.74 2.22 Part BTO's 17.22 5.40 6.955.18 Prod Rate (lbs/hr) 26.5 26.3 24.9 20.8 Residence Time (hrs) 3.313.33 3.45 4.06 C2 Partial Pressure (psia) 220.2 220.5 220.3 220.0 C2Partial Pressure (Bar) 14.99 15.01 14.99 14.98 H2/C2 Conc Ratio (ppm/m%) 4.61 3.84 3.74 3.74 C6/C2 Conc Ratio (m/m) 0.01527 0.01539 0.018350.01729 Ethylene (mole %) 61.03 61.05 61.34 61.26 Isopentane (mole %)12.06 12.16 12.35 12.35 Nitrogen (mole %) 26.75 26.56 26.47 26.58Isopentane Feed (lb/hr) 12.01 12.01 12.01 12.01 RX Pressure (psig)349.07 349.06 349.19 349.18 Rxn Temperature (° C.) 85.00 84.99 85.0085.00 Bed Weight (lbs) 87.6 87.8 85.9 84.2 Bed Level (ft) 6.43 6.23 7.418.19 Continuity Additive Conc (ppmw prod) 54.4 73.4 75.3 90.3 TrimSolution Flow (g/hr) 120.0 79.7 Trim Catalyst Flow (g/hr) 0.0180 0.0119Slurry Cat Flowrate 9.50 10.00 7.00 7.00 Slurry Cat Inner Tube IC5 Flow(lb/hr) 3.01 3.00 3.00 3.00 Slurry Cat Inner Tube N2 Flow (lb/hr) 5.005.00 5.00 5.00 Slurry Cat Outer Tube IC5 Flow (lb/hr) 12.01 12.01 12.0112.01 Slurry Cat Outer Tube N2 Flow (lb/hr) 5.02 5.01 5.02 5.00 PlenumFlow (lb/hr) 62.01 62.56 58.42 56.40 Melt Index (dg/min) 0.73 0.49 1.681.01 MI-5 (dg/min) 2.12 1.38 5.75 3.10 High Load Melt Index (dg/min)18.2 11.7 83.2 37.0 MFR (HLMI/MI) 25.0 23.9 49.4 36.6 MFR I21/I5 8.6 8.414.5 11.9 Density (g/cc) 0.9201 0.9194 0.9340 0.9281 Bulk Density(lb/ft{circumflex over ( )}3) 24.00 24.50 32.40 31.43 Poured BulkDensity (g/cc) 0.3846 0.3926 0.5192 0.5037 Cat Prod (matl Bal) 7,8017,373 9,956 8,300 Polymerization Example 4B 4A 5B 5A Trim MetalloceneIV-C IV-C IV-D IV-D Base Catalyst SD-(III) SD-(III) SD-(III) SD-(III)Part Bed Turnovers Averaging Data 2.13 3.00 2.12 2.63 Part BTO's 5.686.00 5.65 5.26 Prod Rate (lbs/hr) 20.6 21.9 20.7 19.2 Residence Time(hrs) 4.22 4.00 4.25 4.56 C2 Partial Pressure (psia) 220.0 220.0 220.0220.2 C2 Partial Pressure (Bar) 14.98 14.97 14.98 14.99 H2/C2 Conc Ratio(ppm/m %) 3.78 3.78 3.80 3.74 C6/C2 Conc Ratio (m/m) 0.01742 0.018230.01614 0.01709 Ethylene (mole %) 60.95 60.79 60.97 61.29 Isopentane(mole %) 12.30 12.31 12.26 12.42 Nitrogen (mole %) 26.46 26.31 26.5826.49 Isopentane Feed (lb/hr) 12.01 12.01 12.01 12.01 RX Pressure (psig)349.19 349.15 349.16 349.16 Rxn Temperature (° C.) 85.00 85.00 85.0085.00 Bed Weight (lbs) 86.9 87.6 87.8 87.6 Bed Level (ft) 7.55 6.96 6.566.74 Continuity Additive Conc (ppmw prod) 91.0 85.5 90.7 97.6 TrimSolution Flow (g/hr) 80.0 120.0 80.0 119.8 Trim Catalyst Flow (g/hr)0.0120 0.0180 0.0120 0.0180 Slurry Cat Flowrate 7.00 7.00 7.00 7.00Slurry Cat Inner Tube IC5 Flow (lb/hr) 3.00 3.00 3.00 3.00 Slurry CatInner Tube N2 Flow (lb/hr) 5.00 5.00 5.00 5.00 Slurry Cat Outer Tube IC5Flow (lb/hr) 12.01 12.01 12.01 12.01 Slurry Cat Outer Tube N2 Flow(lb/hr) 5.04 5.02 5.02 5.03 Plenum Flow (lb/hr) 55.29 56.68 58.46 58.70Melt Index (dg/min) 1.23 1.72 0.914 1.090 MI-5 (dg/min) 3.59 5.22 2.5283.101 High Load Melt Index (dg/min) 35.9 57.0 21.3 27.8 MFR (HLMI/MI)29.1 33.1 23.3 25.5 MFR I21/I5 10.0 10.9 8.4 9.0 Density (g/cc) 0.92740.9315 0.9221 0.9238 Bulk Density (lb/ft{circumflex over ( )}3) 30.0330.93 30.33 31.42 Poured Bulk Density (g/cc) 0.4813 0.4956 0.4861 0.5036Cat Prod (matl Bal) 8,233 8,767 8,267 7,680 Polymerization Example 6B 6A3C-1 3C-2 Trim Metallocene V-A V-A IV-A/B IV-A/B Base Catalyst SD-(III)SD-(III) SD-(III) SD-(III) Part Bed Turnovers Averaging Data 1.40 1.881.02 1.38 Part BTO's 4.19 5.02 3.07 3.46 Prod Rate (lbs/hr) 20.4 18.129.7 20.0 Residence Time (hrs) 4.30 4.78 2.93 4.34 C2 Partial Pressure(psia) 219.7 220.0 221.2 220.0 C2 Partial Pressure (Bar) 14.96 14.9815.06 14.98 H2/C2 Conc Ratio (ppm/m %) 3.76 3.75 3.55 3.77 C6/C2 ConcRatio (m/m) 0.01595 0.01724 0.01692 0.01953 Ethylene (mole %) 61.0261.03 61.47 60.84 Isopentane (mole %) 12.29 12.43 12.21 12.09 Nitrogen(mole %) 26.72 26.35 26.32 26.47 Isopentane Feed (lb/hr) 12.02 12.0112.02 12.02 RX Pressure (psig) 349.15 349.12 349.18 349.17 RxnTemperature (° C.) 85.00 85.00 84.99 85.00 Bed Weight (lbs) 87.9 86.587.1 86.8 Bed Level (ft) 6.71 7.01 6.81 7.15 Continuity Additive Conc(ppmw prod) 91.7 103.6 63.2 93.7 Trim Solution Flow (g/h) 100.0 150.080.0 80.0 Trim Catalyst Flow (g/hr) 0.0150 0.0225 0.0120 0.0120 SlurryCat Flowrate 7.00 7.00 7.50 5.00 Slurry Cat Inner Tube IC5 Flow (lb/hr)3.00 3.00 3.01 3.00 Slurry Cat Inner Tube N2 Flow (lb/hr) 5.00 5.00 5.005.00 Slurry Cat Outer Tube IC5 Flow (lb/hr) 12.02 12.01 12.02 12.02Slurry Cat Outer Tube N2 Flow (lb/hr) 5.02 5.03 4.99 5.03 Plenum Flow(lb/hr) 59.81 59.74 66.36 65.32 Melt Index (dg/min) 0.602 0.702 0.4010.287 MI-5 (dg/min) 1.640 1.994 1.183 0.851 High Load Melt Index(dg/min) 14.6 19.0 13.4 10.8 MFR (HLMI/MI) 24.3 27.1 33.5 37.8 MFRI21/I5 8.9 9.5 11.4 12.7 Density (g/cc) 0.9201 0.9234 0.9232 0.9206 BulkDensity (lb/ft{circumflex over ( )}3) 30.25 30.77 30.80 32.40 PouredBulk Density (g/cc) 0.4848 0.4930 0.4936 0.5192 Cat Prod (matl Bal)8,178 7,233 11,076 11,200

While the foregoing is directed to embodiments of the present invention,other and further embodiments of the invention can be devised withoutdeparting from the basic scope thereof, and the scope thereof isdetermined by the claims that follow.

1. A method of polymerizing olefins to produce a polyolefin polymer witha multimodal composition distribution, comprising contacting ethyleneand a comonomer with a catalyst system, wherein the catalyst systemcomprises a first catalyst compound and a second catalyst compound thatare co-supported to form a commonly supported catalyst system, whereinthe first catalyst compound comprises the following formula:(C₅H_(a)R¹ _(b))(C₅H_(c)R² _(d))HfX₂ wherein each R¹ is independently H,a hydrocarbyl group, a substituted hydrocarbyl group, or a heteroatomgroup; each R² is independently H, a hydrocarbyl group, a substitutedhydrocarbyl group, or a heteroatom group; a and c are ≧3; a+b=c+d=5; atleast one R¹ and at least one R² is a hydrocarbyl or substitutedhydrocarbyl group; adjacent groups R¹ and R² groups may be coupled toform a ring; and each X is independently a leaving group selected from alabile hydrocarbyl, substituted hydrocarbyl, or heteroatom group, or adivalent radical that links to an R¹ or R² group; and the secondcatalyst compound comprises the following formula:

wherein each R³ is independently H, a hydrocarbyl group, a substitutedhydrocarbyl group, or a heteroatom group; R⁴ is a hydrocarbyl group, asubstituted hydrocarbyl group, or a heteoatom group; each R⁵ isindependently H, a hydrocarbyl group, a substituted hydrocarbyl group,or a heteroatom group; wherein R³, R⁴, and R⁵ may be the same ordifferent; and each X is independently a leaving group selected from alabile hydrocarbyl, a substituted hydrocarbyl, a heteroatom group, or adivalent radical that links to an R³, R⁴, or R⁵ group.
 2. The method ofclaim 1, wherein the value of a comonomer/ethylene incorporation ratiofor the second catalyst is less than about 0.8 as large ascomonomer/ethylene incorporation ratio of the first catalyst.
 3. Themethod of claim 1, wherein the value of the comonomer/ethyleneincorporation ratio for the second catalyst is less than about 0.25 aslarge as a comonomer/ethylene incorporation ratio of the first catalyst.4. (canceled)
 5. (canceled)
 6. The method of claim 1, comprisingcontinuously combining a catalyst component slurry with a catalystcomponent solution to form the commonly supported catalyst system. 7.The method of claim 6, wherein the catalyst component slurry comprisesthe first catalyst compound and the catalyst component solutioncomprises the second catalyst compound.
 8. (canceled)
 9. (canceled) 10.(canceled)
 11. (canceled)
 12. (canceled)
 13. (canceled)
 14. (canceled)15. The method of claim 1, comprising adjusting a ratio of the comonomerto ethylene within a polymerization reactor to control a compositiondistribution, a molecular weight distribution, a melt index (I₂), or aratio of two melt indices, or any combinations thereof, of thepolyolefin polymer.
 16. (canceled)
 17. A catalyst composition comprisinga first catalyst compound and a second catalyst compound that areco-supported forming a commonly supported catalyst system, wherein thefirst catalyst compound comprises the following formula:(C₅H_(a)R¹ _(b))(C₅H_(c)R² _(d))HfX₂ wherein each R¹ is independently H,a hydrocarbyl group, a substituted hydrocarbyl group, or a heteroatomgroup; each R² is independently H, a hydrocarbyl group, a substitutedhydrocarbyl group, or a heteroatom group; a and c are ≧3; a+b=c+d=5; atleast one R¹ and at least one R² is a hydrocarbyl or substitutedhydrocarbyl group; adjacent groups R¹ and R² groups may be coupled toform a ring; and each X is independently a leaving group selected from alabile hydrocarbyl, substituted hydrocarbyl, or heteroatom group, or adivalent radical that links to an R¹ or R² group; and the secondcatalyst compound comprises the following formula:

wherein each R³ is independently H, a hydrocarbyl group, a substitutedhydrocarbyl group, or a heteroatom group; R⁴ is a hydrocarbyl group, asubstituted hydrocarbyl group, or a heteoatom group; each R⁵ isindependently H, a hydrocarbyl group, a substituted hydrocarbyl group,or a heteroatom group; wherein R³, R⁴, and R⁵ may be the same ordifferent; wherein R³, R⁴, or R⁵ groups may be joined with R³, R⁴, or R⁵groups on an opposing cyclopentadienyl structure to form one or morebridges if the number of atoms connecting the two cyclopentadienyl ringsis ≧3; and each X is independently a leaving group selected from alabile hydrocarbyl, a substituted hydrocarbyl, a heteroatom group, or adivalent radical that links to a R³, R⁴, or R⁵ substituent.
 18. Thecatalyst composition of claim 17, wherein the second catalyst compoundcomprises at least one compound with the following formula:


19. The catalyst composition of claim 17, wherein the second catalystcompound comprises at least one compound with the following formula:


20. The catalyst composition of claim 17, wherein the second catalystcompound comprises at least one compound with the following formula:

wherein each R⁴ is independently a methyl, ethyl, propyl, pentyl, hexyl,octyl, nonyl, dodecyl, phenethyl, or other hydrocarbyl.
 21. The catalystcomposition of claim 17, wherein the second catalyst compound comprisesat least one compound with the following formula:


22. The catalyst composition of claim 17, wherein the second catalystcompound comprises at least one compound with the following formula:


23. The catalyst composition of claim 17, wherein the second catalystcompound comprises at least one compound with the following formula:


24. The catalyst composition of claim 17, wherein the first catalystcompound has the following formula:


25. The catalyst composition of claim 17, wherein the first catalystcompound has the following formula:


26. The catalyst composition of claim 17, wherein the ratio of the firstcatalyst compound to the second catalyst compound is between about 10:1to 1:10.
 27. The catalyst composition of claim 17, wherein the ratio ofthe first catalyst compound to the second catalyst compound is betweenabout 3:1 to 1:3.
 28. (canceled)
 29. (canceled)
 30. (canceled) 31.(canceled)
 32. (canceled)
 33. (canceled)
 34. (canceled)
 35. (canceled)36. (canceled)
 37. (canceled)
 38. (canceled)
 39. (canceled) 40.(canceled)
 41. The catalyst composition of claim 17, comprising anorganometallic agent comprising a compound of the following formula: ER⁶_(n)R⁷ _(V-n), wherein E is Al, B, Mg, Ca, Zn, Si, Ti, Zr, Hf; each R⁶is independently H, or a hydrocarbyl; each R⁷ is independently a H, a C1to C20 hydrocarbon group, or a heteroatom containing group having up totwenty carbon atoms, silicon, germanium, tin, lead, or phosphorus; V isthe valence of E, and n is 1-V.
 42. (canceled)
 43. (canceled) 44.(canceled)
 45. The catalyst composition of claim 17, further comprisinga catalyst compound of the following formula:

wherein M is Ti, Zr, or Hf; wherein R⁹ is H, a hydrocarbyl group, asubstituted hydrocarbyl group, or a heteroatom group; and wherein eachR⁹ may be joined together to form a ring; wherein each R¹⁰ isindependently H, a hydrocarbyl group, a substituted hydrocarbyl group,or a heteroatom group.
 46. The catalyst composition of claim 17, furthercomprising at least one Group 15 containing catalyst compoundrepresented by the formula:

wherein: M is a Group 4, 5, or 6 metal; y is 0 or 1, wherein when y is0, group L′ is absent; n is the oxidation state of M; m is the formalcharge of the ligand represented by YZL and YZL; L, L′, Y and Z are eacha Group 15 element; each R¹¹ and R¹² is independently a hydrocarbylgroup, a substituted hydrocarbyl group, or a heteroatom group; R¹³ isabsent or is H, a hydrocarbyl group, a substituted hydrocarbyl group, ora heteroatom group; each R¹⁴ and R¹⁵ is independently a hydrocarbylgroup, an aryl group, substituted aryl group, a cyclic alkyl group, asubstituted cyclic alkyl group, a cyclic arylalkyl group, a substitutedcyclic arylalkyl group or multiple ring system; each R¹⁶ and R¹⁷ isindependently a hydrocarbyl group, a substituted hydrocarbyl group, or aheteroatom group; and R* is absent, or is hydrogen, a Group 14 atomcontaining group, a halogen, or a heteroatom containing group. 47.(canceled)